CN115228451B - Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal - Google Patents

Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal Download PDF

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CN115228451B
CN115228451B CN202210889522.6A CN202210889522A CN115228451B CN 115228451 B CN115228451 B CN 115228451B CN 202210889522 A CN202210889522 A CN 202210889522A CN 115228451 B CN115228451 B CN 115228451B
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sintering
porous ceramic
ceramic material
temperature
rare earth
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CN115228451A (en
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谢耀
欧阳森林
崔振红
杨少华
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Ganzhou Bulai Texin Resource Co ltd
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Abstract

The invention belongs to the technical field of rare earth hydrometallurgy, and particularly relates to a porous ceramic material, a preparation method thereof and application thereof in fluoride ion removal. The invention provides a porous ceramic material, which is prepared from the following components in percentage by mass: 48 to 88.2 percent of lanthanum cerium carbonate, 0.6 to 12 percent of aluminum oxide, 0.6 to 12 percent of silicon dioxide, 4 to 40 percent of calcium carbonate and 0.1 to 10 percent of adhesive. When the porous ceramic material provided by the invention is used for treating the leaching liquid in the rare earth magnetic material waste recovery process, fluoride ions in the leaching liquid can be effectively removed, and meanwhile, the content of rare earth ions in the leaching liquid can not be reduced, so that the recovery rate of the rare earth ions is improved. Compared with the traditional chemical precipitation defluorination method, the method is green, environment-friendly, low in cost, low in rare earth loss rate, high in defluorination efficiency and capable of being recycled for a long time.

Description

Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal
Technical Field
The invention belongs to the technical field of rare earth hydrometallurgy, and particularly relates to a porous ceramic material, a preparation method thereof and application thereof in fluoride ion removal.
Background
Rare earth magnetic materials, especially third generation products of rare earth permanent magnets, are developed very rapidly after the advent of sintered NdFeB (NdFeB), and the yield is increased year by year. During the production and machining process of the rare earth magnetic material, a large amount of leftover materials, cut and ground scraps, abrasive materials and other waste materials are produced, which account for about 30 percent of the total mass of the raw materials, and the waste materials contain Nd, fe, B and other elements, wherein the Nd mass content is about 26 percent, the Dy mass content is about 1 percent, and the rare earth materials face the waste materialsRecovery of Nd from rare earth magnetic materials in a large environment with increasing rare earth prices 2 O 3 And Dy 2 O 3 Has higher economic value.
At present, the conventional recovery method of the waste materials of the rare earth magnetic materials is dressing and smelting treatment, and then leaching liquid is extracted to separate neodymium and dysprosium. However, the composition of the leaching solution is complex, and especially fluoride ions in the leaching solution are extremely harmful to an extraction system. In the extraction process, due to the continuous circulation of the organic phase, fluoride ions and rare earth ions which are jointly extracted into the organic phase continuously form a rare earth fluoride complex, and part of the rare earth fluoride complex forms a third phase and becomes a slag phase in an extraction tank; the other part of the organic phase is followed to reach the back extraction section, so that the product qualification rate is affected; and partial fluoride ion complex cannot be removed through high acid complete back extraction, so that the viscosity of an extracted organic phase, the load of target elements in the organic phase and the phase separation time are permanently influenced, and further the extraction and separation processes and the process indexes of the subsequent processes are influenced, and the removal of harmful impurities represented by fluorine is always a difficult point in the extraction process in the waste recovery process of the rare earth magnetic material.
The current main fluorine removal process is a chemical precipitation method for removing fluorine: the pH value of the leaching solution is adjusted by lime water, calcium fluoride is generated by fluorine and calcium, and then the fluorine ions in the rare earth feed liquid are removed by solid-liquid separation, but the process causes serious exceeding of the calcium ions in the rare earth feed liquid, and certain adjustment slag is generated when the pH value is adjusted, so that the slag contains high rare earth content and the rare earth loss rate is high.
Disclosure of Invention
The invention aims to provide a porous ceramic material, a preparation method thereof and application thereof in fluoride ion removal.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a porous ceramic material, which comprises the following components in percentage by mass:
48 to 88.2 percent of lanthanum cerium carbonate, 0.6 to 12 percent of aluminum oxide, 0.6 to 12 percent of silicon dioxide, 4 to 40 percent of calcium carbonate and 0.1 to 10 percent of adhesive.
Preferably, the particle size of the porous ceramic material is 1-10 mm.
The invention provides a preparation method of the porous ceramic material, which comprises the following steps:
wet mixing the preparation raw material with water to obtain granules;
granulating the granulating material to obtain granules;
and sintering the granular material to obtain the porous ceramic material.
Preferably, the sintering includes sequentially performing a first sintering and a second sintering; the temperature of the first sintering is 300-500 ℃, and the heat preservation time of the first sintering is 1-2 h; the temperature of the second sintering is 1000-1500 ℃, and the heat preservation time of the second sintering is 4-6 h.
Preferably, the rate of temperature rise from room temperature to the temperature of the first sintering and the rate of temperature rise from the temperature of the first sintering to the temperature of the second sintering are independently 5 to 20 ℃/min.
Preferably, before the wet mixing, the preparation raw materials of the porous ceramic material are subjected to pretreatment; the pretreatment comprises the following steps:
mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide, and presintering to obtain a precursor material; the temperature of the presintering is 800-1000 ℃, and the heat preservation time of the presintering is 1-4 h;
grinding the precursor material to obtain precursor powder; the particle size of the precursor powder is less than or equal to 0.15mm;
and mixing the precursor powder, calcium carbonate and an adhesive.
Preferably, the mass ratio of the preparation raw materials of the porous ceramic material to water is (2-4): 1.
The invention provides the application of the porous ceramic material or the porous ceramic material prepared by the preparation method in the technical scheme in fluoride ion removal.
Preferably, the application is: adopting the porous ceramic material as a solid filler to obtain a fixed bed reactor; fluoride ions are removed by passing a liquid containing fluoride ions through the fixed bed reactor.
The invention provides a defluorination fixed bed reactor, wherein solid filler in the defluorination fixed bed reactor is the porous ceramic material according to the technical scheme or the porous ceramic material prepared by the preparation method according to the technical scheme.
The invention provides a porous ceramic material, which comprises the following components in percentage by mass: 48 to 88.2 percent of lanthanum cerium carbonate, 0.6 to 12 percent of aluminum oxide, 0.6 to 12 percent of silicon dioxide, 4 to 40 percent of calcium carbonate and 0.1 to 10 percent of adhesive. The porous ceramic material provided by the invention is prepared from alumina serving as a reinforcing component, silicon dioxide serving as a curing agent, and calcium carbonate serving as a foaming agent and an adhesive during sintering, wherein lanthanum cerium carbonate is used as a main raw material component within the mass percentage content range; wherein lanthanum oxide and cerium oxide formed by lanthanum cerium carbonate can adsorb fluoride ions to form a complex, so that the fluoride ions can be separated and removed efficiently. When the porous ceramic material provided by the invention is used for treating the leaching liquid in the rare earth magnetic material waste recovery process, fluoride ions in the leaching liquid can be effectively removed, and meanwhile, the content of rare earth ions in the leaching liquid can not be reduced, so that the recovery rate of the rare earth ions is improved. Compared with the traditional chemical precipitation defluorination method, the method is green, environment-friendly, low in cost, low in rare earth loss rate, high in defluorination efficiency and capable of being recycled for a long time. The results of the examples show that compared with the chemical precipitation method for removing fluorine, the chemical precipitation method for removing fluorine once can reduce the concentration of fluorine ions from 2g/L to 0.3g/L, and the secondary fluorine removal can be reduced to 0.05g/L; the fluorine ion mass concentration of the porous ceramic material provided by the invention is less than or equal to 0.03g/L after the porous ceramic material is subjected to fluorine removal for 3-5 times continuously, so that the lower-level production quality requirement is met; and the original chemical precipitation method removes fluorine, the mass percentage of rare earth elements in the primary callback slag is 3-7wt%, and the loss rate of the rare earth elements after the porous ceramic material removes fluorine is less than or equal to 0.5%, so that the loss rate of the rare earth elements is effectively reduced.
The invention provides a preparation method of the porous ceramic material, which comprises the following steps: wet mixing the preparation raw material with water to obtain granules; granulating the granulating material to obtain granules; and sintering the granular material to obtain the porous ceramic material. The preparation method provided by the invention is simple and suitable for industrial production, and the porous ceramic material is obtained by sequentially carrying out wet mixing, granulating and sintering.
Further, the sintering comprises the steps of sequentially performing first sintering and second sintering; the temperature of the first sintering is 300-500 ℃, and the heat preservation time of the first sintering is 1-2 h; the temperature of the second sintering is 1000-1500 ℃, and the heat preservation time of the second sintering is 4-6 h. According to the preparation method provided by the invention, the specific implementation mode and sintering parameters of sintering are regulated, soft granules obtained by granulating after wet mixing can be sintered into hard ceramic granules, and the specific surface area of the ceramic material can be effectively enlarged when calcium carbonate is fully decomposed to form a fluffy structure in the sintering process by a fractional sintering mode and controlling the parameters of twice sintering, and meanwhile, porous ceramic materials with developed internal pore structures are formed under the combined action of silicon dioxide, aluminum oxide and bonding, so that lanthanum cerium carbonate can be used as a main material, and fluoride ions in fluorine-containing feed liquid can be effectively removed by adsorbing fluoride ions through the pore structure of the ceramic material.
Detailed Description
The invention provides a porous ceramic material, which comprises the following components in percentage by mass:
48 to 88.2 percent of lanthanum cerium carbonate, 0.6 to 12 percent of aluminum oxide, 0.6 to 12 percent of silicon dioxide, 4 to 40 percent of calcium carbonate and 0.1 to 10 percent of adhesive.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The preparation raw materials of the porous ceramic material comprise 48-88.2% of lanthanum cerium carbonate, preferably 48.5-88% of lanthanum cerium carbonate, and more preferably 50-85% of lanthanum cerium carbonate.
In the invention, lanthanum oxide and cerium oxide obtained by sintering lanthanum cerium carbonate can carry out complexation reaction with fluoride ions so as to fix the fluoride ions.
In the present invention, the lanthanum cerium carbonate is derived from a large amount of a lanthanum cerium carbonate mixture that cannot be sold in a rare earth separation plant. The invention uses lanthanum cerium carbonate as the preparation raw material of the porous ceramic material, expands the application of lanthanum cerium carbonate and has a certain positive effect on the application of lanthanum cerium rare earth.
The preparation raw materials of the porous ceramic comprise 0.6-12% of aluminum oxide, preferably 2-11.5% of aluminum oxide, and more preferably 3-11.3% of aluminum oxide.
In the invention, the aluminum oxide is used as the reinforcing component, so that the strength of the porous ceramic material can be improved, and the porous ceramic material can be recycled for multiple times.
The preparation raw materials of the porous ceramic provided by the invention comprise 0.6-12% of silicon dioxide, preferably 2-11.5%, and more preferably 3-11.3% by mass.
In the invention, the silicon dioxide is used as a curing agent to accelerate the curing and forming of the preparation raw material.
The preparation raw materials of the porous ceramic comprise 4-40% of calcium carbonate, preferably 5-39.5%, and more preferably 8-39.5% by mass.
In the invention, the calcium carbonate is used as a foaming agent, can form a fluffy structure and promotes the formation of a pore structure in the porous ceramic material.
The raw materials for preparing the porous ceramic comprise 0.1-10% of adhesive, preferably 0.2-9% of adhesive, and more preferably 0.5-8.5% of adhesive.
In the present invention, the adhesive is preferably a resin, more preferably an epoxy resin.
In the invention, the adhesive can bond and shape the preparation raw materials.
In the present invention, the porous ceramic material is preferably spherical in shape.
In the present invention, the particle size of the porous ceramic material is preferably 1 to 10mm, particularly preferably 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, and 10mm.
The invention provides a preparation method of the porous ceramic material, which comprises the following steps:
wet mixing the preparation raw materials of the porous ceramic material with water to obtain granules;
granulating the granulating material to obtain granules;
and sintering the granular material to obtain the porous ceramic material.
The preparation raw materials of the porous ceramic material are wet mixed with water to obtain granules.
In the present invention, the present invention preferably further comprises, before the wet mixing, subjecting the raw materials for preparing the porous ceramic material to a pretreatment; the pretreatment preferably comprises the steps of:
mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide (hereinafter referred to as first mixing) and then presintering to obtain a precursor material; the temperature of the presintering is 800-1000 ℃, and the heat preservation time of the presintering is 1-4 h;
grinding the precursor material to obtain precursor powder; the particle size of the precursor powder is less than or equal to 0.15mm;
the precursor powder, calcium carbonate and binder are mixed (hereinafter referred to as second mixing).
In the present invention, the first mixing is preferably performed in a mixer.
In the present invention, the time of the first mixing is preferably 10 to 60 minutes, more preferably 15 to 40 minutes.
In the present invention, the temperature of the pre-sintering is preferably 800 to 1000 ℃, more preferably 850 to 1000 ℃.
In the present invention, the pre-sintering is preferably performed for a holding time of 1 to 4 hours, more preferably 1.5 to 3.5 hours.
In the present invention, the pre-sintering is preferably performed in a muffle furnace.
The present invention preferably removes impurities in the lanthanum cerium carbonate, aluminum oxide and silicon dioxide by the pre-sintering, and simultaneously achieves preliminary bonding of three of lanthanum cerium carbonate, aluminum oxide and silicon dioxide.
In the present invention, the grinding is preferably performed in a Raymond mill.
In the invention, the grinding material is preferably screened after grinding to obtain precursor powder; the mesh size of the screen used for screening is 100 meshes.
The invention has no special requirements for the implementation of the second mixing.
In the invention, the mass ratio of the preparation raw materials of the porous ceramic material to water is (2-4): 1.
The invention has no special requirements on the specific implementation process of the wet mixing.
After the granules are obtained, the invention granulates the granulation material to obtain the granules.
In the present invention, the granulation is preferably performed in a ball making machine.
In the present invention, the particulate material is preferably spherical particulate material.
In the present invention, the particle size of the granule is preferably 1 to 10mm.
After the granular material is obtained, the porous ceramic material is obtained by sintering the granular material.
In the present invention, the sintering is preferably performed in a muffle furnace.
In the present invention, the sintering preferably includes sequentially performing a first sintering and a second sintering.
In the present invention, the temperature of the first sintering is preferably 300 to 500 ℃, more preferably 350 to 500 ℃.
In the present invention, the holding time of the first sintering is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours.
In the present invention, the temperature rise rate from the room temperature to the temperature of the first sintering is preferably 5 to 20 ℃/min, and particularly preferably 5 ℃/min, 10 ℃/min, 20 ℃/min.
In the present invention, the temperature of the second sintering is preferably 1000 to 1500 ℃, more preferably 1050 to 1450 ℃.
In the present invention, the holding time of the second sintering is preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours.
In the present invention, the rate of temperature rise from the temperature of the first sintering to the temperature of the second sintering is preferably 5 to 20 ℃/min, and particularly preferably 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min.
The invention provides the application of the porous ceramic material or the porous ceramic material prepared by the preparation method in the technical scheme in fluoride ion removal.
In the present invention, the application is: adopting the porous ceramic material as a solid filler to obtain a fixed bed reactor; fluoride ions are removed by passing a liquid containing fluoride ions through the fixed bed reactor.
In the present invention, the fixed bed reactors are preferably connected in series in the application.
In the present invention, the number of the fixed bed reactors connected in series is preferably 5.
In the present invention, porous ceramic particles having particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, and 10mm are distributed in order from low to high in each of the fixed bed reactors.
In the present invention, the thickness of the porous ceramic particles of any one particle diameter in each of the fixed bed reactions is preferably 5cm.
In the invention, the lower end outlet of the former fixed bed reactor is communicated with the upper end inlet of the latter fixed bed reactor, and fluorine-containing feed liquid preferably enters from the upper end feed inlet of the 1 st fixed bed reactor.
In the invention, the fluorine ion-containing liquid is leaching liquid obtained by dressing and smelting rare earth material waste.
In the invention, the leaching solution obtained by dressing and smelting the rare earth material waste is preferably: and (3) sequentially carrying out oxidation roasting and hydrochloric acid optimal dissolution on the rare earth material waste to obtain leaching liquid.
Before the extraction separation is carried out on the leaching solution, the fixed bed reactor provided by the invention is preferably adopted for defluorination.
In the present invention, the flow rate of the fluorine ion-containing liquid into the fixed bed reactor is preferably 100 to 150mL/min.
In the present invention, the fluoride ion-containing liquid is preferably pumped by a peristaltic pump when entering the fixed bed reactor.
The invention provides a defluorination fixed bed reactor, wherein solid filler in the defluorination fixed bed reactor is the porous ceramic material according to the technical scheme or the porous ceramic material prepared by the preparation method according to the technical scheme.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 2500g of lanthanum cerium carbonate, 100g of aluminum oxide and 100g of silicon dioxide, mixing and stirring for 20min uniformly by a stirrer, pre-sintering in a muffle furnace at a pre-roasting temperature of 800 ℃ for 2h, and grinding by a Raymond mill and sieving by a 100-mesh sieve to obtain precursor powder; 2000g of precursor powder, 250g of calcium carbonate and 200g of epoxy resin are weighed and uniformly mixed to obtain a mixed premix, and the solid-liquid ratio is 2:1 (mass ratio) adding a water stirrer, stirring for 10min to obtain pasty raw materials, preparing spherical particles with the particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm by using a ball making machine, preparing 200g of spherical particles with the particle diameters of 1-10 mm according to each specification, placing the spherical particles into a muffle furnace, sintering, linearly heating the muffle furnace to 300 ℃ from room temperature according to 20 ℃/min, preserving heat for 1.5h, and heating the muffle furnace to 1300 ℃ according to 10 ℃/min, and sintering for 4h to obtain the porous ceramic particles.
Application example 1
Selecting 5 hollow glass cylinders with the diameter of 10cm and the height of 50cm, and the serial numbers of No. 1, no. 2, no. 3, no. 4 and No. 5, paving the porous ceramic particles prepared in the embodiment 1 in each glass cylinder from small to large according to the particle size, filling the ceramic particles with 10 particle size specifications in each glass cylinder according to the particle size, paving the ceramic particles with the thickness of 5cm in each glass cylinder, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder by using a hose, and the like, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder, taking 1000mL of rare earth 150g/L feed liquid, pumping the ceramic particles from the top of the No. 1 cylinder by using a peristaltic pump with the particle size of 100mL/min, and sequentially passing through the No. 1-5 cylinders. The fluorine concentration of the initial feed liquid is 2.8g/L, and the fluorine concentration is 1g/L after passing through a No. 1 column; passing through a No. 2 column, wherein the fluorine concentration is 0.4g/L; passing through a No. 3 column, wherein the fluorine concentration is 0.09g/L; passing through a column 4, wherein the fluorine concentration is 0.04g/L; passing through a No. 5 column, the fluorine concentration is 0.02g/L, and the final rare earth concentration of the feed liquid is 149g/L.
The rare earth element types and the percentage (wt%) of each rare earth raw material in the total amount of rare earth elements in the feed liquid in this application example are shown in table 1.
TABLE 1 rare earth composition in feed solution
Example 2
Taking 2000g of lanthanum cerium carbonate, 350g of aluminum oxide and 350g of silicon dioxide, mixing and stirring for 20min uniformly by a stirrer, pre-sintering in a muffle furnace at a pre-roasting temperature of 900 ℃ for 4h, and grinding by a Raymond mill and sieving by a 100-mesh sieve to obtain precursor powder; 2000g of precursor powder, 100g of calcium carbonate and 200g of epoxy resin are weighed and uniformly mixed to obtain a mixed premix, and the solid-liquid ratio is 3:1 (mass ratio) adding a water stirrer, stirring for 10min to obtain pasty raw materials, preparing spherical particles with the particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm by using a ball making machine, preparing 200g of spherical particles with the particle diameters of 1-10 mm according to each specification, placing the spherical particles into a muffle furnace, sintering, linearly heating the muffle furnace to 300 ℃ from room temperature according to 5 ℃/min, preserving heat for 1.5h, and then heating the muffle furnace to 1400 ℃ according to 15 ℃/min, and sintering for 4h to obtain the porous ceramic particles.
Application example 2
Selecting 5 hollow glass cylinders with the diameter of 10cm and the height of 50cm, and the serial numbers of No. 1, no. 2, no. 3, no. 4 and No. 5, paving the porous ceramic particles prepared in the embodiment 1 in each glass cylinder from small to large according to the particle size, filling the ceramic particles with 10 particle size specifications in each glass cylinder according to the particle size, paving the ceramic particles with the thickness of 5cm in each glass cylinder, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder by using a hose, and the like, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder, taking 150g/L of rare earth feed liquid with the concentration of 1000mL, pumping the ceramic particles from the top of the No. 1 cylinder by using a peristaltic pump with the concentration of 150mL/min, and sequentially passing through the No. 1-5 cylinders. The fluorine concentration of the initial feed liquid is 2.8g/L, and the fluorine concentration is 1.5g/L after passing through the No. 1 column; passing through a No. 2 column, wherein the fluorine concentration is 0.8g/L; passing through a No. 3 column, wherein the fluorine concentration is 0.3g/L; passing through a column 4, wherein the fluorine concentration is 0.08g/L; passing through a No. 5 column, the fluorine concentration is 0.05g/L, and the final rare earth concentration of the feed liquid is 148g/L. The rare earth element types and the percentage (wt%) of each rare earth raw material in the total amount of rare earth elements in the feed liquid in this application example are shown in table 1.
Example 3
Taking 2300g of lanthanum cerium carbonate, 200g of aluminum oxide and 200g of silicon dioxide, mixing and stirring for 20min uniformly by a stirrer, pre-sintering in a muffle furnace at a pre-roasting temperature of 1000 ℃ for 2h, and grinding by a Raymond mill and sieving by a 100-mesh sieve to obtain precursor powder; 2000g of precursor powder, 250g of calcium carbonate and 200g of epoxy resin are weighed and uniformly mixed to obtain a mixed premix, and the solid-liquid ratio is 4:1 (mass ratio) adding a water stirrer, stirring for 10min to obtain pasty raw materials, preparing spherical particles with the particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm by using a ball making machine, preparing 200g of spherical particles with the particle diameters of 1-10 mm according to each specification, placing the spherical particles into a muffle furnace, sintering, linearly heating the muffle furnace to 300 ℃ from room temperature according to 10 ℃/min, preserving heat for 1.5h, and heating the muffle furnace to 1500 ℃ according to 20 ℃/min, and sintering for 6h to obtain the porous ceramic particles. The rare earth element types and the percentage (wt%) of each rare earth raw material in the total amount of rare earth elements in the feed liquid in this application example are shown in table 1.
Application example 3
Selecting 5 hollow glass cylinders with the diameter of 10cm and the height of 50cm, and the serial numbers of No. 1, no. 2, no. 3, no. 4 and No. 5, paving the porous ceramic particles prepared in the embodiment 1 in each glass cylinder from small to large according to the particle size, filling the ceramic particles with 10 particle size specifications in each glass cylinder according to the particle size, paving the ceramic particles with the thickness of 5cm in each glass cylinder, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder by using a hose, and the like, connecting the bottom of the No. 1 cylinder with the top of the No. 2 cylinder, taking 1000mL of rare earth 150g/L feed liquid, pumping the ceramic particles from the top of the No. 1 cylinder by using a peristaltic pump with the particle size of 100mL/min, and sequentially passing through the No. 1-5 cylinders. The fluorine concentration of the initial feed liquid is 2.8g/L, and the fluorine concentration is 0.8g/L after passing through a No. 1 column; passing through a No. 2 column, wherein the fluorine concentration is 0.1g/L; passing through a No. 3 column, wherein the fluorine concentration is 0.03g/L; passing through a column 4, wherein the fluorine concentration is 0.03g/L; passing through a No. 5 column, the fluorine concentration is 0.02g/L, and the final rare earth concentration of the feed liquid is 149g/L. The rare earth element types and the percentage (wt%) of each rare earth raw material in the total amount of rare earth elements in the feed liquid in this application example are shown in table 1.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (9)

1. The porous ceramic material is characterized by comprising the following raw materials in percentage by mass:
48-88.2% of lanthanum cerium carbonate, 0.6-12% of aluminum oxide, 0.6-12% of silicon dioxide, 4-40% of calcium carbonate and 0.1-10% of adhesive;
the preparation method of the porous ceramic material comprises the following steps:
wet mixing the preparation raw material with water to obtain granules; before the wet mixing, the preparation raw materials are subjected to pretreatment; the pretreatment comprises the following steps: mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide, and presintering to obtain a precursor material; the temperature of the pre-sintering is 800-1000 ℃, and the heat preservation time of the pre-sintering is 1-4 hours; grinding the precursor material to obtain precursor powder; the particle size of the precursor powder is less than or equal to 0.15mm; mixing the precursor powder, calcium carbonate and an adhesive;
granulating the granulating material to obtain granules;
sintering the granular material to obtain the porous ceramic material; the sintering comprises the steps of sequentially performing first sintering and second sintering; the temperature of the first sintering is 300-500 ℃, and the temperature of the second sintering is 1000-1500 ℃.
2. The porous ceramic material according to claim 1, wherein the particle size of the porous ceramic material is 1-10 mm.
3. A method of preparing a porous ceramic material according to claim 1 or 2, comprising the steps of:
wet mixing the preparation raw material with water to obtain granules; before the wet mixing, the preparation raw materials are subjected to pretreatment; the pretreatment comprises the following steps: mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide, and presintering to obtain a precursor material; the temperature of the pre-sintering is 800-1000 ℃, and the heat preservation time of the pre-sintering is 1-4 hours; grinding the precursor material to obtain precursor powder; the particle size of the precursor powder is less than or equal to 0.15mm; mixing the precursor powder, calcium carbonate and an adhesive;
granulating the granulating material to obtain granules;
sintering the granular material to obtain the porous ceramic material; the sintering comprises the steps of sequentially performing first sintering and second sintering; the temperature of the first sintering is 300-500 ℃, and the temperature of the second sintering is 1000-1500 ℃.
4. The method according to claim 3, wherein the first sintering is performed for a heat preservation time of 1 to 2 hours; and the heat preservation time of the second sintering is 4-6 hours.
5. The production method according to claim 4, wherein a rate of temperature rise from room temperature to the temperature of the first sintering and a rate of temperature rise from the temperature of the first sintering to the temperature of the second sintering are independently 5 to 20 ℃/min.
6. The method according to claim 3, wherein the mass ratio of the raw materials to water is (2-4): 1.
7. The porous ceramic material of claim 1 or 2 or the porous ceramic material prepared by the preparation method of any one of claims 3-6, and the application thereof in fluoride ion removal.
8. The use according to claim 7, characterized in that the use is: the porous ceramic material is adopted as solid filler of a fixed bed reactor; fluoride ions are removed by passing a liquid containing fluoride ions through the fixed bed reactor.
9. The defluorination fixed bed reactor is characterized in that the solid filler in the defluorination fixed bed reactor is the porous ceramic material according to claim 1 or 2 or the porous ceramic material prepared by the preparation method according to any one of claims 3-6.
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