CN111270092B - Method for decomposing mixed rare earth ore - Google Patents
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Abstract
The invention discloses a method for decomposing mixed rare earth ore, which comprises the following steps: (1) mixing the mixed rare earth ore with a first sulfuric acid solution with the concentration of 35-85 wt% to obtain slurry I, heating the slurry I to 100-140 ℃ for reaction, and simultaneously condensing and absorbing steam generated by the reaction; carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching solution I and acid leaching residue I; (2) mixing the acid leaching residue I with a second sulfuric acid solution with the concentration of 65-85 wt% to obtain a slurry II, heating the slurry II to 150-300 ℃ for reaction, and simultaneously condensing and absorbing steam generated by the reaction; and carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II. The method of the present invention can reduce the decomposition temperature of the mixed rare earth ore and the concentration of the sulfuric acid solution used.
Description
Technical Field
The invention relates to a method for decomposing mixed rare earth ore.
Background
The mixed rare earth mineral is a main source of global rare earth, wherein baotianbaiyuneboite is the most famous in China. Baotobaiyunebo ore is a rare earth ore deposit which is proved to have the largest reserve and exploitation amount in the world at present, contains rich rare earth resources and is a mixed rare earth ore of bastnaesite and monazite. Due to the complexity of the composition, the smelting separation technology of the mixed rare earth minerals has great difficulty.
At present, the industrialized process for treating the mixed rare earth minerals mainly comprises a concentrated sulfuric acid high-temperature roasting decomposition process and a concentrated alkali liquor normal-pressure decomposition process. The concentrated sulfuric acid high-temperature roasting decomposition process has low requirement on the grade of rare earth ore, short process flow, less consumption of chemical raw materials, and easy large-scale production, and is widely adopted by production enterprises. However, this process produces large amounts of acid tail gas (SO) 2 、SO 3 、H 2 SO 4 、HF、SiF 4 ) And the obtained sulfate wastewater and the radioactive waste residues are difficult to treat, so that the whole environment-friendly treatment engineering system is huge. The concentrated alkali liquor normal pressure decomposition process has no harmful gas and small waste residue. However, the process has high requirements on the level of rare earth minerals, and is easy to generate a large amount of wastewater and cause the loss of rare earth. In addition, the production process of the process is discontinuous, the decomposition time is long, and the wastewater (containing NaOH and Na) 3 PO 4 、NaF、Na 2 CO 3 、Na 2 SO 4 And NaCl) has a great difficulty in recovering, resulting in waste of resources such as fluorine, phosphorus and the like.
CN1031103349A discloses a method for decomposing Bayan obo rare earth ore concentrate at low temperature by acid-base combination. The bayan obo rare earth ore concentrate is added into hydrochloric acid and aluminum chloride, leaching is carried out at 85 ℃, the fluorocarbon acid rare earth salt is dissolved, and the monazite slag is not dissolved. The fluorine in the leachate is present in the form of a complex. Precipitating the complex by a double-salt precipitation method, then filtering, and decomposing the rare earth double salt and monazite by microwave heating by an alkaline method. The method avoids the generation of a large amount of acid gas, but the problems of fluorine resource recycling and aluminum chloride recycling are not solved.
CN109136590A discloses a decomposition treatment process of Baotou mixed rare earth concentrate. And carrying out activated roasting on the Baotou mixed rare earth concentrate for 1-6 hours at the temperature of 350-600 ℃ to obtain activated roasted ore. The activated roasted ore is leached by 3-8 mol/L hydrochloric acid solution to obtain rare earth chloride solution and hydrochloric acid leaching residue. And washing and dehydrating the hydrochloric acid leaching residue to obtain dehydrated leaching residue and a washing solution. And mixing and roasting the dehydrated leaching slag and concentrated sulfuric acid to obtain roasted sulfuric acid ore. The rare earth sulfate aqueous solution is obtained by the procedures of water leaching, neutralization, impurity removal and the like of the roasted sulfuric acid ore. The process comprises a roasting process of a mixture containing dehydrated leaching residues and concentrated sulfuric acid, so that the decomposition of sulfuric acid cannot be avoided, and tail gas is still acid tail gas containing fluorine and sulfur.
CN1847419A discloses a method for decomposing Baotou rare earth concentrate by roasting rare earth sulfate by a step method, which comprises the following steps: (1) mixing the Baotou rare earth concentrate with concentrated sulfuric acid; (2) roasting at 100-320 ℃ for 1-7 hours, and performing water spraying cooling on the generated gas; (3) roasting the solid material at 600-850 ℃ for 1-4 hours, absorbing part of harmful gas by 80-92 wt% of concentrated sulfuric acid, transferring the absorbed concentrated sulfuric acid to the step (1), cooling part of gas by cooling water in the step (2), and transferring the solid material to the next procedure. The sulfuric acid solution used in the process is concentrated sulfuric acid, and the hydrogen fluoride tail gas generated in roasting still contains SO 2 、SO 3 And H 2 SO 4 Acid mist, resulting in low hydrofluoric acid content as a by-product. In addition, the roasting temperature is high, the energy consumption is high, and the concentrated sulfuric acid is decomposed to generate a large amount of SO 3 . Furthermore, the process uses less sulfuric acid, does not form slurry well, causes uneven reaction, and is easy to cause formation of a large amount of solid on the inner wall of equipment.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a method for decomposing a misch metal, which can reduce the decomposition temperature of the misch metal and the concentration of a sulfuric acid solution used. Thus reducing energy consumption, reducing decomposition of sulfuric acid solution and greatly reducing SO 2 、SO 3 And H 2 SO 4 Amount of acid mist generated. In addition, the purity of the by-product hydrofluoric acid can be higher. Further, the method of the invention can realize the recycling of the sulfuric acid solution.
The invention achieves the above purpose through the following technical scheme.
The invention provides a method for decomposing mixed rare earth ore, which comprises the following steps:
(1) mixing the mixed rare earth ore with a first sulfuric acid solution with the concentration of 35-85 wt% to obtain slurry I, heating the slurry I to 100-140 ℃ for reaction, and simultaneously condensing and absorbing steam generated by the reaction; carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching solution I and acid leaching residue I; wherein the rare earth ore is mixed with H in the first sulfuric acid solution 2 SO 4 The weight ratio of (1: 1.5) - (8);
(2) mixing the acid leaching residue I with a second sulfuric acid solution with the concentration of 65-85 wt% to obtain a slurry II, heating the slurry II to 150-300 ℃ for reaction, and simultaneously condensing and absorbing steam generated by the reaction; carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II; wherein, the dry residue of the acid leaching residue I and H in the second sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-8.
According to the method of the present invention, preferably, in the step (1), the mixed rare earth ore contains a rare earth fluoride and a rare earth phosphate.
According to the method of the invention, in the step (1), the reaction time is preferably 10-280 min.
According to the method of the present invention, preferably, in the step (1), the vapor generated by the reaction is condensed and absorbed to obtain hydrofluoric acid as a byproduct.
According to the method of the present invention, preferably, in the step (2), the reaction temperature is 150 to 250 ℃.
According to the method of the present invention, preferably, in the step (2), the reaction temperature is 150 to 200 ℃.
According to the method, in the step (2), the reaction time is preferably 20-280 min; in the step (2), steam generated by the reaction is condensed and absorbed to obtain condensed water.
The method according to the present invention preferably further comprises the steps of:
and adjusting the acid leaching solution II to a sulfuric acid concentration of 65-85 wt% by using concentrated sulfuric acid, and using the acid leaching solution II to decompose the next batch of acid leaching residues I.
The method according to the present invention preferably further comprises the steps of:
washing the acid leaching residue II with the condensed water and deionized water respectively to obtain a filter cake and a washing liquid; leaching the filter cake with water to obtain water leaching residue and water leaching solution; and neutralizing the water leaching solution to remove impurities to obtain a rare earth sulfate aqueous solution.
The method according to the present invention preferably further comprises the steps of:
and combining the washing liquid and the pickle liquor I to obtain a combined liquid, and regulating the combined liquid to the sulfuric acid concentration of 35-85 wt% by using concentrated sulfuric acid for decomposing the next batch of mixed rare earth ore.
The method adopts sulfuric acid solution with mass concentration not more than 85 wt% to decompose the mixed rare earth ore in stages, and the reaction decomposition temperature is controlled to be 100-140 ℃ and 150-300 ℃ respectively. The method of the invention can reduce the decomposition temperature and the concentration of the sulfuric acid solution, thereby reducing the energy consumption, reducing the decomposition of the sulfuric acid solution and greatly reducing the SO 2 、SO 3 And H 2 SO 4 Amount of acid mist generated. In addition, the method can ensure that the purity of the byproduct hydrofluoric acid is higher, and can realize the recycling of the sulfuric acid solution.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In the present invention, "wt%" means weight percentage.
The method of the invention comprises the following steps: (1) a first stage decomposition reaction step; (2) a second stage decomposition reaction step; (3) and (3) treating the acid leaching residue II and the acid leaching solution II. As described in detail below.
< first stage decomposition reaction step >
The method comprises the step of mixing the mixed rare earth ore with a first sulfuric acid solution with the concentration of 35-85 wt% to obtain slurry I, wherein the mixed rare earth ore and H in the first sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-8. Thus being beneficial to reducing the concentration of the sulfuric acid solution, reducing the decomposition temperature and reducing the decomposition of the sulfuric acid solution, SO that SO 2 、SO 3 And H 2 SO 4 The generation amount of the acid mist is greatly reduced, so that the amount of sulfuric acid-containing solution in the byproduct hydrofluoric acid is lower, and the byproduct hydrofluoric acid with higher purity is obtained. The process flow diagram is shown in figure 1.
In the present invention, the misch metal ore contains rare earth fluoride and rare earth phosphate. Examples of misch metal include, but are not limited to, mixed ores formed from bastnaesite and monazite ores. The mischmetal ore is preferably Baotou mischmetal ore concentrate, the REO content is 50-65 wt%, and the CaO content is 6-12 wt%.
In the present invention, the misch metal ore is mainly composed of bastnaesite and monazite. The invention discovers that the bastnaesite is rare earth fluorocarbon salt, the decomposition temperature of the bastnaesite in a sulfuric acid solution is low, and the bastnaesite can be decomposed by using a first sulfuric acid solution with the mass concentration of 35-85 wt% at 100-140 ℃; the monazite ore is rare earth phosphate which is more stable than the bastnaesite, and can be decomposed only by using a sulfuric acid solution with the mass concentration of more than 65 wt% and the reaction temperature of more than 150 ℃.
In the present invention, the concentration of the first sulfuric acid solution may be 35 to 85 wt%, preferably 40 to 80 wt%, and more preferably 40 to 75 wt%. SO that SO can be reacted 2 、SO 3 And H 2 SO 4 The generation amount of acid mist is greatly reduced.
Mixing rare earth ore with H in first sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-8, preferably 1: 1.5-6, and more preferably 1: 1.6-5. This can help the sulfuric acid solution to form slurry I with the mixed rare earth ore and help to decompose the rare earth fluoride at lower temperatures. With solid-phase reactions of the prior artIn contrast, the present invention is a reaction in a slurry state. In the invention, the materials are uniformly mixed, the reaction is more uniform, and a large amount of solid can not be formed on the inner wall of the equipment.
In the present invention, the mixed rare earth ore may be stirred when being mixed with the first sulfuric acid solution. This can make the raw materials mix evenly.
Heating the slurry I to 100-140 ℃ for reaction, and condensing and absorbing steam generated by the reaction. Preferably, the reaction is carried out by heating to 100-135 ℃. More preferably, the reaction is carried out by heating to 100-130 ℃. Stirring is also carried out during the reaction, so that the reaction can be more uniform. The reaction time is 10-280 min. Preferably, the reaction time is 10-240 min. More preferably, the reaction time is 15 to 240 min. Thus, the rare earth fluoride in the mixed rare earth ore can be completely decomposed, and the decomposition of the sulfuric acid solution (the sulfuric acid solution is hardly decomposed) caused by overhigh temperature can be avoided, thereby greatly reducing SO 2 、SO 3 And H 2 SO 4 The amount of acid mist generated is low, so the amount of sulfuric acid in the obtained by-product hydrofluoric acid is low, and the purity of the hydrofluoric acid is higher.
And condensing and absorbing steam generated by the reaction to obtain a byproduct hydrofluoric acid. The hydrofluoric acid obtained by the method has higher purity and can be directly used.
And after the reaction is finished, carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching solution I and acid leaching residue I. In the present invention, the solid-liquid separation may be centrifugation or filtration. Filtration is preferred. The acid leaching solution I can be adjusted to a sulfuric acid concentration of 35-85 wt% by concentrated sulfuric acid (the concentration of the concentrated sulfuric acid is not less than 90 wt%), preferably adjusted to a sulfuric acid concentration of 40-80 wt%, and more preferably adjusted to a sulfuric acid concentration of 40-75 wt%. And the regulated pickle liquor I is used for decomposing the next batch of mixed rare earth ore. Thus realizing the recycling of the sulfuric acid solution. And the acid leaching residue I is used as a raw material for the second stage decomposition reaction.
< second-stage decomposition reaction step >
Mixing the acid leaching residue I with a second sulfuric acid solution with the concentration of 65-85 wt% to obtain a slurry II, wherein the dry residue of the acid leaching residue I and H in the second sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-8. The weight of the dry residue of the acid leaching residue I is the weight of the acid leaching residue I after water is removed. Thus being beneficial to reducing the decomposition reaction temperature, reducing the decomposition of sulfuric acid solution and greatly reducing SO 3 The amount of production of (c).
And (3) mixing the acid leaching residue I with a second sulfuric acid solution with the concentration of 65-85 wt% to obtain a slurry II, and stirring and uniformly mixing. The concentration of the second sulfuric acid solution may be 65 to 85 wt%, preferably 65 to 80 wt%, and more preferably 65 to 75 wt%. This helps to reduce decomposition of the sulfuric acid solution.
The dry residue of the acid leaching residue I and H in the sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) may be 1:1.5 to 8, preferably 1:1.5 to 6, and more preferably 1:1.5 to 5. This helps to lower the decomposition reaction temperature.
Heating the slurry II to 150-300 ℃ for reaction. Preferably, the reaction is carried out by heating to 150-250 ℃. More preferably, the reaction is carried out by heating to 150-200 ℃. The reaction time is 20-280 min, preferably 25-260 min. More preferably 30 to 240 min. Thus being beneficial to reducing the energy consumption of the reaction and the decomposition of the sulfuric acid solution, and hardly generating SO 2 、SO 3 And H 2 SO 4 And (4) acid mist. Further, the method can realize effective separation of phosphate radical and rare earth element, and avoid the influence of phosphate radical on the recovery of rare earth element (rare earth ion).
And condensing and absorbing steam generated by the second-stage decomposition reaction to obtain condensed water. The resulting condensate can still be reused.
And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II. In the present invention, the solid-liquid separation may be centrifugation or filtration. Filtration is preferred. Thus, the phosphate radical can be separated from the rare earth ions, and the phosphate radical can be dissolved in the acid leaching solution II, and the rare earth ions exist in the acid leaching residue II.
< treatment Steps of acid-leached slag II and acid-leached liquid II >
And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II. Adjusting the concentration of the obtained pickle liquor II with concentrated sulfuric acid (the concentration of the concentrated sulfuric acid is not less than 90 wt%) to 65-85 wt%, preferably 65-80 wt%, and more preferably 65-75 wt%. And the regulated acid leaching solution II is used for decomposing the next batch of acid leaching slag I. Therefore, the recycling of the sulfuric acid solution can be realized, the environment is protected, and the cost is saved.
In the invention, the obtained acid leaching residue II is treated, and the method comprises the following steps:
and washing the acid leaching residue II with the condensed water and the deionized water obtained in the second-stage decomposition reaction step respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching residue and a water leaching solution. And neutralizing the water leaching solution to remove impurities to obtain a rare earth sulfate aqueous solution. The rare earth sulfate aqueous solution can be obtained by neutralizing and removing impurities from the water leaching solution by adopting a method which is conventional in the field, and is not described in detail herein.
And (4) determining the content of the rare earth in the water leaching residue, and calculating to obtain the REO decomposition rate.
The REO decomposition rate (REO content in the misch metal ore-REO content in the water leaching slag)/(REO content in the misch metal ore) x 100%.
The lower the content of the rare earth in the water leaching slag, the higher the decomposition rate of REO, namely the higher the decomposition efficiency of the sulfuric acid solution for pulping and sectionally decomposing the mixed rare earth ore. In the invention, the REO decomposition rate is not less than 95.5%.
And combining the washing liquid and the pickle liquor I to obtain a combined liquid, and adjusting the combined liquid to a sulfuric acid concentration of 35-85 wt%, preferably 40-80 wt%, and more preferably 40-75 wt% by using concentrated sulfuric acid (the concentration of the concentrated sulfuric acid is not less than 90 wt%). The adjusted combined solution can be used for decomposing the next batch of mixed rare earth ore. In the present invention, the pickling solution I may or may not be combined with the washing solution, and it is preferable to combine the pickling solution I with the washing solution.
According to the temperature window and the reaction efficiency difference of decomposing the bastnaesite and the monazite by the sulfuric acid solution, the rare earth fluoride and the rare earth phosphate are decomposed step by controlling the temperature by a program and controlling the concentration of the sulfuric acid solution and the dosage of the sulfuric acid solution (the sulfuric acid solution is in absolute excess), so that the rare earth element can be almost completely separated from the fluorine resource and the phosphorus resource, and conditions are created for respectively recovering the fluorine resource and the phosphorus resource. Specifically, rare earth fluoride is decomposed at 100-140 ℃, the sulfuric acid solution is hardly decomposed, and components in tail gas (steam) are purified to obtain high-purity hydrofluoric acid which can be directly utilized without subsequent treatment. The rare earth phosphate is independently decomposed at 150-300 ℃, after decomposition, rare earth ions mainly exist in the acid leaching residue II, phosphate ions mainly exist in the acid leaching solution II, other impurities in the acid leaching solution II are few, phosphate can be enriched through recycling of the acid leaching solution II, and then phosphorus resources are comprehensively utilized. And the acid leaching residue II is treated to obtain the rare earth sulfate aqueous solution with high purity. Thus, the separation of the phosphate radical and the rare earth ions after the rare earth phosphate is decomposed can be realized, and the influence of the phosphate radical on the rare earth ions is avoided.
The invention realizes the recycling of the sulfuric acid solution and is more environment-friendly. During recycling, the sulfuric acid concentration of the acid leaching solution I and the acid leaching solution II is adjusted by supplementing concentrated sulfuric acid, so that the use standard of the invention is met, and the REO decomposition rate can still be kept between 95.7 and 98.5 percent when the acid leaching solution I and the acid leaching solution II are recycled for 5 to 8 times.
In the following examples, the REO decomposition rate is (REO content in misch metal ore-REO content in water-leached slag)/(REO content in misch metal ore) × 100%.
Example 1
The misch metal ore used in this example is Baotou misch metal concentrate, in which the REO content is 61.66 wt%, and the CaO content is 6.19 wt%.
100kg of Baotou misch metal concentrate was uniformly mixed with 375kg of a first sulfuric acid solution (40 wt% concentration) (Baotou misch metal concentrate and H) 2 SO 4 The weight ratio of the raw materials is 1:1.5) to obtain slurry I, heating the slurry I to 100 ℃, reacting for 240min, and condensing and absorbing generated steam to obtain a byproduct hydrofluoric acid. And carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching residue I and acid leaching solution I. Wherein the acid leaching residue I is 57.2kg, and the water content is 18.1%.
57.2kg of acid-leaching residue I were mixed homogeneously with 268kg of a second sulfuric acid solution (70% strength by weight) (dry residue of acid-leaching residue I with H) 2 SO 4 In a weight ratio of 1:4) to obtain a slurryAnd II, heating the slurry II to 170 ℃, reacting for 120min, and absorbing generated steam through condensation to obtain condensed water. And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II.
And washing the acid leaching residue II with the obtained condensed water and deionized water respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching slag and a water leaching solution, and neutralizing and removing impurities from the water leaching solution to obtain a rare earth sulfate aqueous solution. The REO content in the water-soaked slag is determined, and the REO decomposition rate is obtained by calculation to be 95.7%.
And combining the obtained washing liquid and the pickle liquor I, adjusting the concentration of sulfuric acid in the combined liquid to be 40 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of Baotou mixed rare earth concentrate.
And regulating the acid leaching solution II to a sulfuric acid concentration of 70 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of acid leaching residue I.
And (4) continuously treating five batches of mixed rare earth concentrates of the Baotou, wherein the REO decomposition rate is 95.5-96.4%.
Example 2
The mischmetal ore used in this example was baotite mischmetal concentrate, in which the REO content was 61.96 wt%, and the CaO content was 6.5 wt%.
100kg of Baotou misch metal concentrate and 588kg of sulfuric acid solution (the concentration is 85 wt%) are uniformly mixed (Baotou misch metal concentrate and H) 2 SO 4 The weight ratio of the raw materials is 1:5) to obtain slurry I, heating the slurry I to 140 ℃, reacting for 15min, and condensing and absorbing generated steam to obtain a byproduct hydrofluoric acid; and carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching residue I and acid leaching solution I. Wherein the acid leaching residue I is 55.3kg, and the water content is 18.7%.
55.3kg of acid leaching residue I and 265kg of sulfuric acid solution (85 wt% concentration) are mixed uniformly (dry residue of acid leaching residue I and H 2 SO 4 The weight ratio of the components is 1:5) to obtain slurry II, heating the slurry II to 190 ℃, reacting for 30min, and absorbing generated steam through condensation to obtain condensed water. And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II.
And washing the acid leaching residue II with the obtained condensed water and deionized water respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching slag and a water leaching solution, and neutralizing and removing impurities from the water leaching solution to obtain a rare earth sulfuric acid aqueous solution. And (4) determining the REO content in the water leaching residue, and calculating to obtain the REO decomposition rate of 98.5%.
And combining the obtained washing liquid and the pickle liquor I, adjusting the concentration of sulfuric acid in the combined liquid to 85 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of Baotou mixed rare earth concentrate.
And regulating the acid leaching solution II to 85 wt% with concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of acid leaching residue I.
And (4) continuously treating eight batches of Baotou mixed rare earth concentrates, wherein the REO decomposition rate is 97.8-98.5%.
Example 3
The misch metal ore used in this example is Baotou misch metal concentrate, in which the REO content is 51.48 wt%, and the CaO content is 10.7 wt%.
100kg of Baotou misch metal concentrate was uniformly mixed with 600kg of a first sulfuric acid solution (concentration of 50 wt%) (Baotou misch metal concentrate and H) 2 SO 4 The weight ratio of the hydrofluoric acid to the water is 1:3) to obtain slurry I, heating the slurry I to 110 ℃, reacting for 180min, and condensing and absorbing generated steam to obtain a byproduct hydrofluoric acid. And carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching residue I and acid leaching solution I. Wherein the acid leaching residue I is 59.6kg, and the water content is 15.3%.
59.6kg of acid-leaching residue I were mixed homogeneously with 117kg of a second sulfuric acid solution (65% strength by weight) (dry residue of acid-leaching residue I with H) 2 SO 4 In a weight ratio of 1:1.5) to obtain slurry II, heating the slurry II to 150 ℃, reacting for 240min, and absorbing generated steam through condensation to obtain condensed water. And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II.
And washing the acid leaching residue II with the obtained condensed water and deionized water respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching slag and a water leaching solution, and neutralizing and removing impurities from the water leaching solution to obtain a rare earth sulfate aqueous solution. The REO content in the water-soaked slag is determined, and the REO decomposition rate is 96.1 percent through calculation.
And combining the obtained washing liquid and the pickle liquor I, adjusting the concentration of sulfuric acid in the combined liquid to be 50 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of Baotou misch metal concentrate.
And regulating the acid leaching solution II to a sulfuric acid concentration of 65 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of acid leaching residue I.
And (4) continuously treating eight batches of Baotou mixed rare earth concentrates, wherein the REO decomposition rate is 95.7-96.6%.
Example 4
The misch metal ore used in this example is Baotou misch metal concentrate, in which the REO content is 61.66 wt%, and the CaO content is 6.19 wt%.
100kg of Baotou misch metal concentrate and 667kg of sulfuric acid solution (concentration of 60 wt%) are mixed uniformly (Baotou misch metal concentrate and H) 2 SO 4 The weight ratio of the raw materials is 1:4) to obtain slurry I, heating the slurry I to 130 ℃, reacting for 30min, and condensing and absorbing generated steam to obtain a byproduct hydrofluoric acid. And carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching residue I and acid leaching solution I. Wherein the acid leaching residue I is 56.5kg, and the water content is 18.6%.
56.5kg of acid leaching residue I and 287kg of sulfuric acid solution (concentration 80 wt%) are mixed uniformly (dry residue of acid leaching residue I and H 2 SO 4 The weight ratio of the components is 1:5) to obtain slurry II, heating the slurry II to 200 ℃, reacting for 60min, and absorbing generated steam through condensation to obtain condensed water. And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II.
And washing the acid leaching residue II with the obtained condensed water and deionized water respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching slag and a water leaching solution, and neutralizing and removing impurities from the water leaching solution to obtain a rare earth sulfate aqueous solution. The REO content in the water-soaked slag is determined, and the REO decomposition rate is obtained by calculation to be 97.7%.
And combining the obtained washing liquid and the pickle liquor I, adjusting the concentration of sulfuric acid in the combined liquid to be 50 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of Baotou misch metal concentrate.
And regulating the acid leaching solution II to a sulfuric acid concentration of 80 wt% by using a concentrated sulfuric acid solution (the concentration is 92 wt%), and decomposing the next batch of acid leaching residue I.
And (4) continuously treating eight batches of mixed rare earth concentrates with the REO decomposition rate of 96.4-97.8%.
Example 5
The misch metal ore used in this example is Baotou misch metal concentrate, in which the REO content is 51.48 wt%, and the CaO content is 10.7 wt%.
100kg of Baotou misch metal concentrate and 571kg of sulfuric acid solution (the concentration is 70 wt%) are uniformly mixed (Baotou misch metal concentrate and H) 2 SO 4 The weight ratio of the raw materials is 1:4) to obtain slurry I, heating the slurry I to 120 ℃, reacting for 60min, and condensing and absorbing generated steam to obtain a byproduct hydrofluoric acid. And carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching residue I and acid leaching solution I. Wherein, the acid leaching residue I is 58.2kg, and the water content is 18.1 percent.
58.2kg of acid leaching residue I and 251kg of sulfuric acid solution (the concentration is 75 wt%) are uniformly mixed (the dry residue of the acid leaching residue I and H 2 SO 4 The weight ratio of the components is 1:4) to obtain slurry II, heating the slurry II to 160 ℃, reacting for 180min, and absorbing generated steam through condensation to obtain condensed water. And carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II. And washing the acid leaching residue II with the obtained condensed water and deionized water respectively to obtain a filter cake and a washing liquid. And (3) leaching the filter cake with water to obtain water leaching slag and a water leaching solution, and neutralizing and removing impurities from the water leaching solution to obtain a rare earth sulfate aqueous solution. The REO content in the water-soaked slag is determined, and the REO decomposition rate is 96.1 percent through calculation.
And combining the obtained washing liquid and the pickle liquor I, adjusting the concentration of sulfuric acid in the combined liquid to be 50 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of Baotou misch metal concentrate.
And regulating the acid leaching solution II to a sulfuric acid concentration of 65 wt% by using concentrated sulfuric acid (the concentration is 92 wt%), and decomposing the next batch of acid leaching residue I.
And (4) continuously treating eight batches of Baotou mixed rare earth concentrates, wherein the REO decomposition rate is 95.7-96.6%.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (6)
1. A method for decomposing mixed rare earth ore is characterized by comprising the following steps:
(1) mixing a mixed rare earth ore containing rare earth fluoride and rare earth phosphate with a first sulfuric acid solution with the concentration of 35-80 wt% to obtain slurry I, heating the slurry I to 100-130 ℃ to react for 15-240 min, and simultaneously condensing and absorbing steam generated by the reaction; carrying out solid-liquid separation on the reacted slurry I to obtain acid leaching solution I and acid leaching residue I; wherein the rare earth ore is mixed with H in the first sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-1.6;
(2) mixing the acid leaching residue I with a second sulfuric acid solution with the concentration of 65-75 wt% to obtain a slurry II, heating the slurry II to 150-200 ℃ for reaction, and simultaneously condensing and absorbing steam generated by the reaction; carrying out solid-liquid separation on the reacted slurry II to obtain acid leaching solution II and acid leaching residue II; separating phosphate radical from rare earth ions, and dissolving the phosphate radical in the acid leaching solution II, wherein the rare earth ions exist in the acid leaching residue II; wherein, the dry residue of the acid leaching residue I and H in the second sulfuric acid solution 2 SO 4 The weight ratio of (A) to (B) is 1: 1.5-5;
the REO decomposition rate is not less than 95.5%.
2. The method of claim 1, wherein in step (1), the vapor generated by the reaction is condensed and absorbed to obtain hydrofluoric acid as a byproduct.
3. The method of claim 1, wherein:
in the step (2), the reaction time is 20-280 min;
in the step (2), steam generated by the reaction is condensed and absorbed to obtain condensed water.
4. A method according to any one of claims 1 to 3, further comprising the steps of:
and regulating the acid leaching solution II to a sulfuric acid concentration of 65-75 wt% by using concentrated sulfuric acid for decomposing the next batch of acid leaching residue I.
5. The method of claim 4, further comprising the steps of:
washing the acid leaching residue II with the condensed water and deionized water respectively to obtain a filter cake and a washing liquid; leaching the filter cake with water to obtain water leaching residue and water leaching solution; and neutralizing the water leaching solution to remove impurities to obtain a rare earth sulfate aqueous solution.
6. The method of claim 5, further comprising the steps of:
and combining the washing liquid and the pickle liquor I to obtain a combined liquid, and regulating the combined liquid to the sulfuric acid concentration of 35-80 wt% by using concentrated sulfuric acid for decomposing the next batch of mixed rare earth ore.
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