CN111115675A - High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof - Google Patents
High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof Download PDFInfo
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Abstract
A high-purity light lanthanum carbonate or lanthanum oxide and a preparation method thereof, the production method at least comprises the following steps: s1, hydrolyzing the lanthanum oxide powder and deionized water to prepare lanthanum hydroxide slurry; s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 to carry out carbonization reaction, so as to obtain lanthanum carbonate slurry; s3, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate; s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 to obtain the high-purity light lanthanum oxide. The lanthanum oxide produced by the method has ultrahigh purity, extremely low impurity content and small apparent density, and can be better used for high-grade new materials such as rare earth magnetic materials, luminescent materials, hydrogen storage materials, crystal materials, catalytic materials and the like.
Description
Technical Field
The invention belongs to the field of high-purity material preparation, and particularly relates to high-purity light lanthanum carbonate or lanthanum oxide and a preparation method thereof.
Background
The rare earth oxide is a key basic material for preparing high-grade new materials such as rare earth magnetic materials, luminescent materials, hydrogen storage materials, crystal materials, catalytic materials and the like. With the continuous expansion of the application field and the level of the rare earth, the quality requirement of high and new materials on rare earth oxide is higher and higher, and the mode of taking account of the physical property control of granularity, purity, morphology, specific surface and the like is changed.
Lanthanum oxide, one of the important rare earth oxides, has a strong ability to gain and lose electrons, is easy to undergo oxidation reaction or reduction reaction, and has been widely applied to catalysts, luminescent materials, permanent magnetic materials, high-performance ceramics and the like.
For many years, people have always searched for suitable process conditions for obtaining more ideal high-purity powder materials. The existing methods for producing high-purity lanthanum oxide have two main types of physical methods and chemical methods: physical methods include vacuum condensation, physical pulverization, mechanical ball milling, and the like; the chemical methods mainly include precipitation, vapor deposition, sol-gel, hydrothermal synthesis, electrochemical method, microemulsion, and polymer protection.
The prior preparation method has the following defects:
although the physical crushing method and the mechanical ball milling method have low investment, simple process and easy control, impurities are easy to be mixed in the crushing process, the product purity is low, the particle shape is unstable, and the uniformity is not good;
the solvent extraction method is adopted, the high-purity rare earth chloride solution obtained by separation and purification is prepared by ammonium bicarbonate precipitation, the chlorine radical and oil content are high, and a large amount of ammonia nitrogen wastewater is generated;
the chemical precipitation method is characterized by that it uses the salt solution (such as nitric acid, hydrochloric acid or sulfuric acid aqueous solution) obtained by dissolving high-purity lanthanum oxide with acid and converting it into lanthanum as raw material, and adopts the precipitation preparation of ammonium hydrogen carbonate and urea, etc. to obtain the invented productWashing the product with water to remove nitrate radical, chloride radical or sulfate radical, filtering, stoving, calcining and crushing to prepare lanthanum oxide powder. The method is the most common method in industry, and the loose specific gravity of the prepared product is generally 1.0-1.5 g/m3. Such as US6387339, discloses the preparation of a soluble lanthanum salt by precipitation of an aqueous solution of a soluble lanthanum salt with an aqueous oxalic acid solution as a precipitant. For another example, chinese patent CN104117682A discloses a method for preparing a rare earth oxide with controllable particle size and narrow distribution, which comprises using single or mixed rare earth solution as raw material, adding into a precipitation reactor together with buffer solution, slowly adding alkali and introducing carbon dioxide gas for carbonization reaction, and controlling the pH value of the reaction system within the buffer range of the buffer solution; or firstly precipitating the rare earth solution into rare earth hydroxide by using alkali, and then introducing carbon dioxide gas for carrying out carbonization reaction; and (3) after the carbonization reaction is finished, obtaining rare earth carbonate slurry, and filtering, washing, drying and roasting the slurry to obtain rare earth oxide.
The existing precipitation methods inevitably introduce impurity ions such as chloride ions, sulfate ions and/or nitrate ions in lanthanum oxide, reduce the purity of the product, and are easy to agglomerate and difficult to filter, so that the product (lanthanum hydroxide/lanthanum carbonate) is difficult to wash and filter, and is easy to filter to cause loss; meanwhile, a large amount of ammonia nitrogen wastewater is generated, so that the standard discharge of the precipitated wastewater can increase the operation cost of enterprises.
In addition, in other common methods in the prior art, such as a vacuum condensation method, a vapor deposition method, a sol-gel method, and the like, although a high-purity material with a clean surface, a regular and controllable particle size, and a good dispersibility can be obtained, the problems of high equipment investment, complex process, and difficult process control exist, and a dispersing agent, an organic complexing agent, a polymer protective agent, and the like are often used in the preparation process to increase the raw material cost.
Disclosure of Invention
Therefore, the invention aims to provide high-purity light lanthanum carbonate or lanthanum oxide, which has high purity and small apparent density.
In order to achieve the purpose, the invention adopts the following technical scheme:
high-purity lightLanthanum carbonate with total content of non-rare earth cations (Ca, Mg, Fe, etc.) less than 0.01%, and anion impurity Cl-、SO4 2-And NO3-The total content is less than 0.01%, preferably 0.005%; the phosphorus content is less than 0.001%, and the loose packed density is 150-700 g/cm3(ii) a And preferably, the loose packing density of the high-purity light lanthanum carbonate is 150-240 mg/cm3。
Preferably, the lanthanum carbonate has a particle size D50Less than 10 μm, and a primary particle diameter of 10 to 100nm, preferably 30 to 100 nm. In this embodiment, D50The primary particle size is the size of the grains, which is the agglomerated particle size.
The invention also discloses high-purity light lanthanum oxide, wherein the total content of non-rare earth cations (Ca, Mg, Fe and the like) is less than 0.015 percent, and anion impurities Cl-、SO4 2-And NO3-The total content is less than 0.01 percent, preferably 0.005 percent, the phosphorus content is less than 0.001 percent, and the loose packed density is 100-600 g/cm3(ii) a And preferably the loose packed density is 100-200 mg/cm3。
Preferably, the particle size D of lanthanum oxide50Less than 10 μm, and a primary particle diameter of 10 to 100nm, preferably 30 to 100 nm.
The lanthanum carbonate or lanthanum oxide provided by the invention has high purity, small apparent density, good particle dispersibility and narrow particle size distribution, and can be prepared by the method provided by the following steps.
One of the purposes of the invention is to provide a preparation method of high-purity light lanthanum carbonate or lanthanum oxide, which at least comprises the following steps:
s1, hydrolyzing the micron-sized lanthanum oxide powder with deionized water to prepare lanthanum hydroxide slurry;
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 to perform carbonization reaction to obtain lanthanum carbonate slurry;
s3, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 to obtain nano-scale high-purity light rare earth oxide lanthanum oxide and carbon dioxide gas.
The preparation method of lanthanum carbonate or lanthanum oxide can realize CO2The method has the advantages that the green house gas is recycled, the low-carbon emission reduction of the rare earth industry is realized, lanthanum oxide powder with the absolute purity of more than 99.0 wt% is used as a raw material, the product of lanthanum carbonate or lanthanum oxide with the absolute purity of more than 99.9 wt% can be prepared, the non-rare earth impurities are obviously reduced, the apparent density is small, and the lanthanum carbonate or lanthanum oxide product is high in purity and light in weight.
The non-rare earth impurities of the 5N lanthanum oxide in the national standard need to be less than 0.02 percent, namely 200ppm, and the absolute content of rare earth is more than 99.0 percent, so that the high-purity light lanthanum oxide obtained by the invention has ultrahigh purity, extremely low impurity content and low apparent density through the matching of the steps of the production method, and can be better used for high-grade new materials such as rare earth magnetic materials, luminescent materials, hydrogen storage materials, crystal materials, catalytic materials and the like.
Preferably, in step S1, the lanthanum oxide powder has an absolute purity of > 99 wt% and is in the micron order. The higher the purity of the initial lanthanum oxide powder is, the more consumption in subsequent treatment can be saved, and a product with higher absolute purity can be obtained. The smaller the initial lanthanum oxide powder particle size, the higher the activity, the better the hydrolysis reaction effect, the preferred particle size is D50＜100μm。
Preferably, in the step S1, the lanthanum oxide powder further includes a step of calcining at a high temperature of 500 to 900 ℃ before hydrolysis. The activity of the hydrolysis reaction can be recovered by the commercial lanthanum oxide through the high-temperature calcination step.
Preferably, in the step S1, the mass ratio of the lanthanum oxide powder to water is 6:1 to 1:1, and preferably 6:1 to 3: 1.
Preferably, in the step S1, the obtained lanthanum hydroxide slurry is sequentially washed by deionized water and/or absolute ethyl alcohol to remove impurity ions. In S1, lanthanum hydroxide is washed for the purpose of removing impurity ions from the lanthanum oxide raw material to improve the purity.
Preferably, in the step S2, the carbonization reaction is carried out by ultrasound, ① can further disperse lanthanum hydroxide and carbon dioxide gas by the aid of ultrasound, ② tiny bubbles generated by ultrasound reduce the specific surface free energy of tiny crystal grains and inhibit aggregation and growth of crystal nuclei, ③ shearing and crushing action of ultrasound microwave flow on the grains can also remove amorphous lanthanum carbonate adhered to undissolved lanthanum hydroxide solids to promote the carbonization reaction to rapidly and effectively proceed, destroy agglomeration among lanthanum carbonate crystal particles and reduce secondary grain size, and parameters such as frequency, power and the like of the ultrasound step can be adjusted according to the reaction condition in actual operation.
Preferably, in the step S2, the step of introducing the carbon dioxide gas is performed in a porous dispersion manner.
Preferably, in step S2, the carbon dioxide gas is boiler flue gas, rare earth carbonate or oxalate roasting kiln gas collected and recovered in the rare earth oxide production process, or is industrial byproduct carbon dioxide gas, or is industrial grade carbon dioxide directly used.
Preferably, in the carbonization reaction in step S2, the concentration of carbon dioxide gas is 10% to 100%, and the molar ratio of rare earth to carbon dioxide is 1:1.5 to 1: 3.
Preferably, in the step S2, the carbonization reaction pressure is normal pressure to 0.4MPa, and the temperature of the reaction system is controlled to be 5 to 60 ℃; the reaction time is controlled to be 0.5-2 hours.
Preferably, in step S2, a dispersant is further added after the carbonization reaction is completed to adjust the surface charge of the particles, so as to obtain a lanthanum carbonate slurry with good dispersibility. The dispersant may be an anionic surfactant and/or a nonionic surfactant; the addition amount of the dispersant is preferably 0.2 to 10 wt%.
Suitable anionic surfactants include combinations of 1 or more than 2 of carboxylates, phosphates, sulfates, sulfonates, and the like; suitable nonionic surfactants include combinations of 1 or 2 or more of alcohol ethoxylates, ethoxylated long chain amines, ethylene glycol, propylene glycol, polyglyceryl esters, alkylamines, fatty acid methyl ester ethoxylates, and the like.
Preferably, in the step S4, the temperature in the baking step is controlled to be 800 to 1000 ℃.
Preferably, the step S4 further includes collecting carbon dioxide gas generated during the roasting of lanthanum carbonate, and returning the collected carbon dioxide gas to the carbonization reaction in S2.
The invention has the following beneficial effects:
(1) the product obtained by the invention has high quality: the method of the invention prepares the nanometer high-purity light product by adopting the steps of direct hydrolysis, carbonization and the like for the micron high-purity lanthanum carbonate or lanthanum oxide, and other impurities are not introduced in the whole reaction process. In the hydrolysis and carbonization processes, trace anions brought in by the raw materials are exposed and dissolved in water due to the transformation of the crystal structure, and can be further removed by filtering and washing. During carbonization, non-rare earth cation impurities such as magnesium, calcium and the like brought in the raw materials can generate soluble bicarbonate so as to be dissolved in water. The non-rare earth impurities of the raw materials can be removed, and the products with low chlorine, low sulfur, low nitrogen, low oil and low apparent density are obtained. The rare earth compound (rare earth carbonate/rare earth oxide) with special physical properties can be widely applied to functional materials such as rare earth ceramic materials, catalytic materials, magnetic materials and the like.
As the lanthanide shrinks, the ionic radius of the lanthanide decreases, resulting in a regular gradient in the properties of the lanthanide as the atomic number increases. The electronic configuration of the outermost two layers of rare earth elements is basically similar, and the rare earth elements show typical metal properties in chemical reaction. Their metallic properties are inferior to those of alkali metals and alkaline earth metals and are more reactive than other metallic elements. The rare earth elements are arranged according to the activity of metals in 17 rare earth elements, and the metal activity of lanthanum is the strongest, so lanthanum oxide reacts to generate lanthanum hydroxide through a hydrolysis method, and other rare earth oxides cannot be prepared through hydrolysis and carbonization and only lanthanum oxide can be prepared.
In the reaction process of the scheme of the invention, the carbonization reaction formula of impurity ions of magnesium, calcium and the like is as follows:
MO+H2O+2CO2＝＝M(HCO3)2；
M(OH)2+2CO2＝＝M(HCO3)2；
wherein M is impurity ion such as magnesium and calcium capable of generating soluble bicarbonate.
(2) The product obtained by the invention has small apparent density, good particle dispersibility and narrow particle size distribution, and the addition of porous dispersed carbon dioxide can keep the reaction stable and effectively prevent agglomeration; and the carbon dioxide released in the roasting decomposition process of the lanthanum carbonate can effectively prevent the high-purity light lanthanum carbonate from agglomerating and hardening. The carbonization reaction steps of the invention have the following specific reaction equations:
La2O3+3H2O＝＝2La(OH)3；
2La(OH)3+3CO2＝＝La2(CO3)3+3H2O；
in the carbonization process, if adopt the haplopore to concentrate and pour into carbon dioxide gas, the carbon dioxide bubble in the solution is big and not of uniform size, only bubble edge and thick liquid contact, the inside carbon dioxide gas of bubble can not take place the reaction immediately, and gas-liquid area of contact is less, has influenced the speed of carbonization reaction, and the crystal nucleus that generates in the solution is less, is favorable to the growth of crystal nucleus, obtains great crystal. Carbon dioxide gas is added in a porous dispersion mode, carbon dioxide bubbles are uniformly dispersed and mixed with the slurry, the specific surface area is large, more lanthanum hydroxide has the opportunity to react with carbon dioxide, the generation of lanthanum carbonate crystal nuclei is facilitated, and high-purity light lanthanum carbonate is obtained.
In the time of the spontaneous formation of the carbonization reaction crystal nucleus, because of no crystal nucleus, a large amount of solute precipitated is not produced on the surface of the crystal nucleus (no crystal nucleus is generated at this time, and a large amount of lanthanum hydroxide exists in the system), but appears in other places in the solution, and through the hydration with water, an amorphous state is formed to reduce the entropy value of the system, and meanwhile, the solute is adhered to the surface of undissolved lanthanum hydroxide particle solid, so that the dissolution of the lanthanum hydroxide is hindered, the contact between the lanthanum hydroxide and carbon dioxide is isolated, and the reaction rate and the effect are reduced. The micro impact force of the carbon dioxide gas can effectively solve the problem and realize the rapid and complete proceeding of the carbonization reaction.
(3) The reaction system of the invention is stable: in the process of producing high-purity lanthanum oxide by using a conventional solution system, in order to ensure the stability of the reaction system, the pH value of the whole reaction system needs to be maintained stable by controlling the reaction feeding conditions or using a buffering agent. In the invention, the pH value in the carbonization system is kept by the solubility of lanthanum hydroxide in a long period of time in the early stage of the reaction, as shown in the following formula, the pH value of the reaction system can be controlled without a feeding mode or other methods, so that the whole reaction is carried out stably, and the granularity and the distribution of precipitated particles can be effectively controlled;
(4) high-efficiency clean production: chemical materials (such as acid, a stabilizer, a buffering agent and the like) are not required to be added in the production process, the method belongs to an atom economic reaction, and efficient and clean production can be realized. The wastewater generated by the process disclosed by the invention is low in salt and ammonia nitrogen, can be directly discharged when meeting the environmental protection requirement, does not need to additionally increase the environmental protection treatment cost, and reduces the operation cost of enterprises; at the same time realize CO2The recycling of greenhouse gases provides technical support for low carbon and emission reduction in the rare earth industry.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
Preparing lanthanum hydroxide slurry: s1, the total content of non-rare earth cations (Ca, Mg, Fe and the like) is 0.070%, the content of anions is 0.10%, the micron-sized lanthanum oxide powder is calcined at the high temperature of 500 ℃ and then hydrolyzed with deionized water according to the mass ratio of 6:1 to prepare lanthanum hydroxide slurry, and the obtained lanthanum hydroxide slurry is repeatedly washed by water to remove impurity ions. The hydrolysis rate of this example was 98.50%.
Example 2
Preparing lanthanum hydroxide slurry: s1 the content of non-rare earth cations (Ca, Mg, Fe, etc.) is 0.055% and the content of anions is 0.10%, the micron lanthanum oxide powder and deionized water are hydrolyzed according to the mass ratio of 4:1 to prepare lanthanum hydroxide slurry, and the obtained lanthanum hydroxide slurry is washed by water to remove impurity ions. The hydrolysis rate of this example was 99.20%.
Example 3
Preparing lanthanum hydroxide slurry: s1, the content of non-rare earth cations (Ca, Mg, Fe and the like) is 0.060 percent in total, the content of anions is 0.12 percent, the micron-sized lanthanum oxide powder is calcined at the high temperature of 800 ℃, then is hydrolyzed with deionized water according to the mass ratio of 3:1 to prepare lanthanum hydroxide slurry, and the obtained lanthanum hydroxide slurry is washed by water to remove impurity ions. The hydrolysis rate of this example was 99.70%.
Example 4
Preparing lanthanum hydroxide slurry: s1, adding non-rare earth cations (Ca, Mg, Fe and the like) 0.059% in total, adding anions 0.11%, and mixing the micron lanthanum oxide powder and deionized water according to the mass ratio of 2: 1, hydrolyzing to prepare lanthanum hydroxide slurry, and washing the obtained lanthanum hydroxide slurry by water to remove impurity ions. The hydrolysis rate of this example was 99.30%.
Example 5
Preparing lanthanum hydroxide slurry: s1, the total content of non-rare earth cations (Ca, Mg, Fe and the like) is 0.049%, the content of anions is 0.09%, and the mass ratio of the micron lanthanum oxide powder to deionized water is 1:1, hydrolyzing to prepare lanthanum hydroxide slurry, and washing the obtained lanthanum hydroxide slurry by ethanol to remove impurity ions. The hydrolysis rate of this example was 98.80%.
Example 6
High purity, light lanthanum carbonate or lanthanum oxide was prepared using the lanthanum hydroxide slurry prepared in example 3:
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1, and carrying out carbonization reaction under ultrasound to obtain lanthanum carbonate slurry;
wherein the concentration of the carbon dioxide gas is 80%, and the molar ratio of the rare earth to the carbon dioxide is 1: 3;
the temperature of the carbonization reaction system is 60 ℃; the reaction time is 2 hours;
s3, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 at 800 ℃ to obtain the high-purity light lanthanum oxide.
Through detection, in the lanthanum carbonate product obtained in the embodiment, the content of non-rare earth cations (Ca, Mg, Fe, and the like) is reduced from 0.060% in the raw materials to 0.008%, the content of anionic impurities is 0.0060%, the content of phosphorus is 0.0008%, and the particle size D is 0505 μm, primary particle diameter of 80nm, and apparent density of 160g/cm3。
The obtained lanthanum oxide had a total content of non-rare earth cations (Ca, Mg, Fe, etc.) of 0.0120%, a total content of anionic impurities of 0.0090%, a phosphorus content of 0.0006%, and a particle diameter D of 0.0006%507 μm, primary particle diameter of 95nm, and apparent density of 100g/cm3。
Example 7
High purity, light lanthanum carbonate or lanthanum oxide was prepared using the lanthanum hydroxide slurry prepared in example 3:
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 in a porous dispersion mode to perform carbonization reaction to obtain lanthanum carbonate slurry;
wherein the concentration of carbon dioxide gas is 99%, and the molar ratio of rare earth to carbon dioxide is 1: 2.5;
the carbonization reaction pressure is 0.4MPa, and the temperature of the reaction system is 40 ℃; the reaction time is 1 hour;
s3, washing, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 at 800 ℃ to obtain the high-purity light lanthanum oxide.
Through detection, in the lanthanum carbonate product obtained in the embodiment, the content of non-rare earth cations (Ca, Mg, Fe, and the like) is reduced from 0.060% in the raw material to 0.007%, the content of anion impurities is 0.0050%, the content of phosphorus is 0.0008%, and the particle size D is the same as that of the lanthanum carbonate product obtained in the previous embodiment502 μm, primary particle diameter of 70nm, and apparent density of 190g/cm3。
The obtained lanthanum oxide contains non-rare earth cations 0.0105% and anions0.0075% of the total impurities, 0.0006% of phosphorus, and particle diameter D503.5 μm, a primary particle diameter of 88nm, and a bulk density of 150g/cm3。
Example 8
High purity, light lanthanum carbonate or lanthanum oxide was prepared using the lanthanum hydroxide slurry prepared in example 3:
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 in a porous dispersion mode, and performing carbonization reaction under ultrasound to obtain lanthanum carbonate slurry and high-purity lanthanum carbonate slurry;
wherein the concentration of carbon dioxide gas is 30%, and the molar ratio of rare earth to carbon dioxide is 1: 2;
the temperature of the carbonization reaction system is 25 ℃; the reaction time is 1 hour;
s3, washing, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate, and collecting carbon dioxide gas generated in the roasting process of the lanthanum carbonate and returning the carbon dioxide gas to be used for the carbonization reaction in S2;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 at 800 ℃ to obtain the high-purity light lanthanum oxide.
Through detection, in the lanthanum carbonate product obtained in the embodiment, the content of non-rare earth cations (Ca, Mg, Fe, and the like) is reduced from 0.060% in the raw material to 0.007%, the content of anion impurities is 0.0050%, the content of phosphorus is 0.0008%, and the particle size D is the same as that of the lanthanum carbonate product obtained in the previous embodiment501.2 μm, a primary particle diameter of 50nm, and a bulk density of 220g/cm3。
The obtained lanthanum oxide contains non-rare earth cation 0.0105%, anion impurity 0.0075%, phosphorus 0.0006%, and particle diameter D502.5 μm, a primary particle diameter of 65nm, and a bulk density of 180g/cm3。
Example 9
High purity, light lanthanum carbonate or lanthanum oxide was prepared using the lanthanum hydroxide slurry prepared in example 2:
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 in a porous dispersion mode to perform carbonization reaction to obtain lanthanum carbonate slurry, and adding a polyethylene glycol dispersant to adjust the surface charge of particles to obtain the lanthanum carbonate slurry with good dispersibility;
wherein the concentration of the carbon dioxide gas is 50%, and the molar ratio of the rare earth to the carbon dioxide is 1: 2;
the temperature of the carbonization reaction system is 10 ℃; the reaction time was 0.5 hours;
s3, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 at 900 ℃ to obtain the high-purity light lanthanum oxide.
Through detection, in the lanthanum carbonate product obtained in the embodiment, the content of non-rare earth cations (Ca, Mg, Fe, and the like) is reduced from 0.055% in the raw material to 0.006%, the content of anionic impurities is 0.0040%, the content of phosphorus is 0.0006%, and the particle size D is 0500.92 μm, primary particle diameter of 30nm, and apparent density of 240g/cm3。
The obtained lanthanum oxide had a non-rare earth cation content of 0.009%, a combined anion impurity content of 0.0060%, a phosphorus content of 0.0005%, and a particle diameter D of 0.0005%501.2 μm, a primary particle diameter of 42nm, and a bulk density of 200g/cm3。
Example 10
High purity, light lanthanum carbonate or lanthanum oxide was prepared using the lanthanum hydroxide slurry prepared in example 2:
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 in a porous dispersion mode, carrying out carbonization reaction under ultrasound to obtain lanthanum carbonate slurry, and adding lauric acid to adjust the surface charge of particles to obtain the lanthanum carbonate slurry with good dispersibility;
wherein, the concentration of carbon dioxide gas is 100%, the molar ratio of rare earth to carbon dioxide is 1: 1.5;
the temperature of the carbonization reaction system is 5 ℃; the reaction time was 0.5 hours;
s3, washing, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 at 1000 ℃ to obtain the high-purity light lanthanum oxide.
Through detection, in the lanthanum carbonate product obtained in the embodiment, the content of non-rare earth cations (Ca, Mg, Fe, and the like) is reduced from 0.055% in the raw material to 0.005%, the content of anionic impurities is 0.003%, the content of phosphorus is 0.0006%, and the particle size D is 0.0006%500.52 μm, primary particle diameter of 10nm, and apparent density of 620g/cm3。
The obtained lanthanum oxide had a non-rare earth cation content of 0.0075%, a total content of anion impurities of 0.0045%, a phosphorus content of 0.0003%, and a particle diameter D of 0.0003%500.9 μm, primary particle diameter of 32nm, and apparent density of 500g/cm3。
Therefore, the lanthanum carbonate product prepared by the method has the non-rare earth cation content of less than 0.01 percent, the anion content of less than 0.01 percent, the phosphorus content of less than 0.001 percent and the granularity D50Less than 10 μm, a primary particle diameter of 10 to 100 μm, and a bulk density of 150 to 700mg/cm3(ii) a The lanthanum oxide product has non-rare earth cation content less than 0.015%, anion content less than 0.01%, phosphorus content less than 0.001%, and granularity D50Less than 10 μm, a primary particle diameter of 10 to 100 μm, and a bulk density of 100 to 600mg/cm3。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A high-purity light lanthanum carbonate contains non-rare earth cations (less than 0.01%) and anionic impurity Cl-、SO4 2-And NO3-The total content is less than 0.01 percent, the phosphorus content is less than 0.001 percent, and the apparent density is 150-700 mg/cm3。
2. The high-purity light lanthanum carbonate according to claim 1,characterized in that the particle size D of the lanthanum carbonate50Less than 10 μm and a primary particle diameter of 10 to 100 nm.
3. High-purity light lanthanum oxide, wherein the content of non-rare earth cations is less than 0.015 percent, and anion impurity Cl-、SO4 2-And NO3-The total content is less than 0.01 percent, the phosphorus content is less than 0.001 percent, and the apparent density is 100-600 mg/cm3。
4. The high purity light lanthanum oxide of claim 3, wherein the lanthanum oxide has a particle size D50Less than 10 μm and a primary particle diameter of 10 to 100 nm.
5. A preparation method of high-purity light lanthanum carbonate or lanthanum oxide at least comprises the following steps:
s1, hydrolyzing the micron-sized lanthanum oxide powder with deionized water to prepare lanthanum hydroxide slurry;
s2, introducing carbon dioxide gas into the lanthanum hydroxide slurry obtained in the step S1 to perform carbonization reaction to obtain lanthanum carbonate slurry;
s3, filtering and drying the lanthanum carbonate slurry obtained in the step S2 to obtain high-purity light lanthanum carbonate;
s4, roasting the high-purity light lanthanum carbonate obtained in the step S3 to obtain the nano-scale high-purity light lanthanum oxide.
6. The method according to claim 5, wherein in the step S1:
calcining the lanthanum oxide powder at a high temperature of 500-900 ℃ before hydrolysis;
the mass ratio of the lanthanum oxide powder to water is 6: 1-1: 1.
7. The production method according to claim 5 or 6, wherein in the step S1:
and washing the obtained lanthanum hydroxide slurry by deionized water and/or absolute ethyl alcohol sequentially to remove impurity ions.
8. The production method according to any one of claims 5 to 7, wherein in step S2, the carbonization reaction is performed with ultrasound; the step of introducing the carbon dioxide gas is in a porous dispersion mode.
9. The production method according to any one of claims 5 to 8, characterized in that in step S2, the carbon dioxide gas is boiler flue gas, rare earth carbonate or oxalate roasting kiln gas collected and recovered in a rare earth oxide production process, or is industrial by-product carbon dioxide gas, or industrial grade carbon dioxide is directly used;
the concentration of the carbon dioxide gas is 10% -100%, and the molar ratio of the rare earth to the carbon dioxide is 1: 1.5-1: 3;
the pressure of the carbonization reaction is normal pressure to 0.4MPa, the temperature of a reaction system is controlled to be 5-60 ℃, and the reaction time is controlled to be 0.5-2 hours;
in step S2, a step of adding a dispersant to adjust the surface charge of the particles after the carbonization reaction is completed is further included to obtain a lanthanum carbonate slurry with good dispersibility.
10. The method according to any one of claims 5 to 9, wherein in the step S4, the temperature of the roasting step is controlled to be 800 to 1000 ℃;
the step S4 further includes a step of collecting carbon dioxide gas generated during the firing of lanthanum carbonate and returning the collected carbon dioxide gas to the carbonization reaction in S2.
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