CN115228451A - 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

Info

Publication number
CN115228451A
CN115228451A CN202210889522.6A CN202210889522A CN115228451A CN 115228451 A CN115228451 A CN 115228451A CN 202210889522 A CN202210889522 A CN 202210889522A CN 115228451 A CN115228451 A CN 115228451A
Authority
CN
China
Prior art keywords
sintering
porous ceramic
ceramic material
percent
rare earth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210889522.6A
Other languages
Chinese (zh)
Other versions
CN115228451B (en
Inventor
谢耀
欧阳森林
崔振红
杨少华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ganzhou Bulai Texin Resource Co ltd
Original Assignee
Ganzhou Bulai Texin Resource Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ganzhou Bulai Texin Resource Co ltd filed Critical Ganzhou Bulai Texin Resource Co ltd
Priority to CN202210889522.6A priority Critical patent/CN115228451B/en
Publication of CN115228451A publication Critical patent/CN115228451A/en
Application granted granted Critical
Publication of CN115228451B publication Critical patent/CN115228451B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

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 porous ceramic material provided by the invention comprises the following components in percentage by mass: 48 to 88.2 percent of cerium lanthanum 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 liquor in the recovery process of the rare earth magnetic material waste, fluorine ions in the leaching liquor can be effectively removed, and meanwhile, the content of rare earth ions in the leaching liquor 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 has the advantages of environmental protection, low cost, low rare earth loss rate, high defluorination efficiency and long-term recycling.

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
The rare earth magnetic material, especially the third generation product of rare earth permanent magnet, sintered neodymium iron boron (NdFeB) is developed rapidly after coming out, and the yield is increased year by year. During the production and machining of the rare earth magnetic material, a large amount of leftover materials, cutting scraps and grinding materials which are cut and ground and the like are produced, the waste materials account for about 30 percent of the total mass of the raw materials, the waste materials contain elements such as Nd, fe, B and the like, the mass content of Nd is about 26 percent, the mass content of Dy is about 1 percent, and the Nd is recovered from the rare earth magnetic material under the resource crisis problem of rare earth and the large environment that the price of the rare earth is increasingly raised 2 O 3 And Dy 2 O 3 Has higher economic value.
At present, the conventional recovery method of the waste of the rare earth magnetic material is dressing and smelting treatment, and then, extracting and separating neodymium and dysprosium from the leachate. But the composition of the leaching solution is complex, and particularly, fluorine ions in the leaching solution have great harm to an extraction system. In the extraction process, because the organic phase is continuously circulated, fluoride ions and rare earth ions which are jointly extracted into the organic phase continuously form a rare earth fluoride complex, and a part of the rare earth fluoride complex forms a third phase to become a slag phase in the extraction tank; the other part reaches a back extraction section along with the organic phase, so that the product percent of pass is influenced; and part of fluoride ion complexes can not be removed by high-acid complete back extraction, which permanently influences the viscosity of an extraction organic phase, the loading of target elements in the organic phase and the phase separation time, and further influences the technological indexes of an extraction separation process and a subsequent process, so that 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 currently mainstream defluorination process is defluorination by a chemical precipitation method: lime water is used for adjusting back the pH value of the leachate, calcium fluoride is generated by fluorine and calcium, and then solid-liquid separation is carried out to remove fluorine ions in the rare earth feed liquid.
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 purpose, the invention provides the following technical scheme:
the invention provides a porous ceramic material which is prepared from the following raw materials in percentage by mass:
48 to 88.2 percent of cerium lanthanum 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 in the technical scheme, which comprises the following steps:
wet mixing the preparation raw materials with water to obtain granulation materials;
granulating the granulated material to obtain a granular material;
and sintering the granules to obtain the porous ceramic material.
Preferably, the sintering comprises 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 increase from room temperature to the temperature of the first sintering and the rate of temperature increase 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 method further comprises the step of pretreating the raw materials for preparing the porous ceramic material; the pretreatment comprises the following steps:
mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide, and then pre-sintering 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 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 raw materials for preparing the porous ceramic material to water is (2-4): 1.
The invention provides the application of the porous ceramic material in the technical scheme or the porous ceramic material prepared by the preparation method in the technical scheme in the removal of fluorine ions.
Preferably, the application is: obtaining a fixed bed reactor by using the porous ceramic material as a solid filler; and (3) flowing the liquid containing the fluoride ions through the fixed bed reactor to remove the fluoride ions.
The invention provides a fluorine-removing fixed bed reactor, wherein solid fillers in the fluorine-removing fixed bed reactor are porous ceramic materials in the technical scheme or porous ceramic materials prepared by the preparation method in 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 cerium lanthanum 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 takes aluminum oxide as a reinforcing component, silicon dioxide as a curing agent, calcium carbonate as a foaming agent and an adhesive during sintering, and takes lanthanum carbonate and cerium carbonate as main raw material components within the mass percentage content range to obtain the porous ceramic material; lanthanum oxide and cerium oxide formed by lanthanum carbonate and cerium carbonate can adsorb fluoride ions to form a complex compound, so that the fluoride ions can be efficiently separated and removed. When the porous ceramic material provided by the invention is used for treating the leaching liquor in the recovery process of the rare earth magnetic material waste, fluorine ions in the leaching liquor can be effectively removed, and meanwhile, the content of rare earth ions in the leaching liquor 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 has the advantages of environmental protection, low cost, low rare earth loss rate, high defluorination efficiency and long-term recycling. The results of the examples show that compared with the chemical precipitation method for removing fluorine, the chemical precipitation method for removing fluorine for the first time can reduce the concentration of fluorine ions from 2g/L to 0.3g/L, and the chemical precipitation method for removing fluorine for the second time can reduce the concentration of fluorine ions to 0.05g/L; the mass concentration of fluorine ions of the porous ceramic material after continuous 3-5 times of fluorine removal is less than or equal to 0.03g/L, so that the quality requirement of the next-stage production is met; and the original chemical precipitation method is used for removing fluorine, the mass percentage of the rare earth elements in the primary tempering slag is 3-7 wt%, the loss rate of the rare earth elements after the fluorine removal of the porous ceramic material is less than or equal to 0.5%, and the loss rate of the rare earth elements is effectively reduced.
The invention provides a preparation method of the porous ceramic material in the technical scheme, which comprises the following steps: wet mixing the preparation raw materials with water to obtain granulation materials; granulating the granulated material to obtain a granulated material; and sintering the granules 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, granulation and sintering.
Further, the sintering of the invention comprises a first sintering and a second sintering which are sequentially carried out; 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, by regulating and controlling the specific implementation mode and sintering parameters of sintering, soft granular materials obtained by granulation after wet mixing can be sintered into hard ceramic particles, and by means of a step-by-step sintering mode and controlling the parameters of two times of sintering, when calcium carbonate is fully decomposed to form a fluffy structure in the sintering process, the specific surface area of a ceramic material is effectively enlarged, and meanwhile, a porous ceramic material with a developed internal pore structure is 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 fluorine ions are effectively adsorbed by the pore structure of the ceramic material to form a complex to remove the fluorine ions in the fluorine-containing feed liquid.
Detailed Description
The invention provides a porous ceramic material, which comprises the following components in percentage by mass:
48 to 88.2 percent of cerium lanthanum 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 the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The raw materials for preparing the porous ceramic material comprise 48 to 88.2 percent of lanthanum cerium carbonate, preferably 48.5 to 88 percent, and more preferably 50 to 85 percent by mass percentage.
In the invention, lanthanum oxide and cerium oxide obtained by sintering the lanthanum carbonate and cerium carbonate can perform a complex reaction with fluorine ions so as to fix the fluorine ions.
In the present invention, the lanthanum cerium carbonate is derived from a large unsaleable mixture of lanthanum cerium carbonate in a rare earth separation plant. The invention takes the lanthanum carbonate cerium as the preparation raw material of the porous ceramic material, expands the application of the lanthanum carbonate cerium and has certain positive effect on the application of the lanthanum cerium rare earth.
The raw material for preparing the porous ceramic comprises, by mass percent, 0.6-12% of alumina, preferably 2-11.5%, and more preferably 3-11.3%.
In the invention, the aluminum trioxide is used as a 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 material of the porous ceramic comprises 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 molding of the preparation raw materials.
The raw materials for preparing the porous ceramic comprise, by mass percent, 4-40% of calcium carbonate, preferably 5-39.5%, and more preferably 8-39.5%.
In the present invention, the calcium carbonate is used as a foaming agent, and can form a fluffy structure to promote the formation of a pore structure in the porous ceramic material.
The raw materials for preparing the porous ceramic comprise, by mass, 0.1-10% of a binder, preferably 0.2-9%, and more preferably 0.5-8.5%.
In the present invention, the adhesive is preferably a resin, and more preferably an epoxy resin.
In the invention, the adhesive can bond and shape the preparation raw materials.
In the present invention, the shape of the porous ceramic material is preferably spherical.
In the present invention, the particle size of the porous ceramic material is preferably 1 to 10mm, and particularly preferably 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, and 10mm.
The invention provides a preparation method of the porous ceramic material in the technical scheme, which comprises the following steps:
wet mixing the preparation raw materials of the porous ceramic material with water to obtain granulated materials;
granulating the granulated material to obtain a granular material;
and sintering the granules to obtain the porous ceramic material.
The preparation raw materials of the porous ceramic material are wet-mixed with water to obtain the granulated material.
In the present invention, before the wet mixing, the present invention preferably further comprises pretreating the raw materials for preparing the porous ceramic material; the pretreatment preferably comprises the following steps:
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 pre-sintering is 800-1000 ℃, and the heat preservation time of the pre-sintering 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-agitator.
In the present invention, the time for the first mixing is preferably 10 to 60min, and more preferably 15 to 40min.
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 holding time for the pre-sintering is preferably 1 to 4 hours, and more preferably 1.5 to 3.5 hours.
In the present invention, the pre-sintering is preferably performed in a muffle furnace.
In the invention, impurities in the lanthanum cerium carbonate, the aluminum oxide and the silicon dioxide are preferably removed through the pre-sintering, and the initial combination of the lanthanum cerium carbonate, the aluminum oxide and the silicon dioxide is realized at the same time.
In the present invention, the grinding is preferably carried out in a Raymond mill.
In the invention, after grinding, the ground material is preferably screened to obtain precursor powder; the sieve used for sieving has 100 meshes.
The invention has no special requirements on the specific implementation process 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 present invention has no particular requirements for the specific implementation of the wet mixing.
After the granulated material is obtained, the granulated material is granulated to obtain the granulated material.
In the present invention, the granulation is preferably performed in a pelletizer.
In the present invention, the particulate material is preferably a spherical particulate material.
In the present invention, the particle size of the particulate material is preferably 1 to 10mm.
After the granules are obtained, the porous ceramic material is obtained by sintering the granules.
In the present invention, the sintering is preferably performed in a muffle furnace.
In the present invention, the sintering preferably includes sequentially performing the first sintering and the 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 for the first sintering is preferably 1 to 2 hours, and more preferably 1.2 to 1.8 hours.
In the present invention, the rate of temperature increase from room temperature to the first sintering temperature is preferably 5 to 20 ℃/min, more preferably 5 ℃/min, 10 ℃/min, or 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 for the second sintering is preferably 4 to 6 hours, and more preferably 4.5 to 5.5 hours.
In the present invention, the rate of temperature increase from the first sintering temperature to the second sintering temperature is preferably 5 to 20 ℃/min, more preferably 5 ℃/min, 10 ℃/min, 15 ℃/min, or 20 ℃/min.
The invention provides the application of the porous ceramic material in the technical scheme or the porous ceramic material prepared by the preparation method in the technical scheme in the removal of fluorine ions.
In the present invention, the applications are: obtaining a fixed bed reactor by using the porous ceramic material as a solid filler; and (3) flowing the liquid containing the fluoride ions through the fixed bed reactor to remove the fluoride ions.
In the present invention, when used, the fixed bed reactors are preferably connected in series.
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 each of the fixed bed reactors in the order from the lower side to the higher side.
In the present invention, each of the fixed bed reactions is preferably performed such that the thickness of the porous ceramic particles of any one particle size is 5cm.
In the invention, the lower end outlet of the previous fixed bed reactor is communicated with the upper end inlet of the next fixed bed reactor, and the fluorine-containing feed liquid preferably enters from the upper end feed inlet of the 1 st fixed bed reactor.
In the invention, the liquid containing the fluoride ions is leachate 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 oxidizing roasting and hydrochloric acid preferential dissolution on the rare earth material waste to obtain a leaching solution.
Before the leachate is subjected to extraction separation, the invention preferably adopts the fixed bed reactor provided by the invention to remove fluorine.
In the present invention, the flow rate of the liquid containing fluoride ions into the fixed bed reactor is preferably 100 to 150mL/min.
In the present invention, the liquid containing fluoride ions is preferably pumped in by a peristaltic pump when entering the fixed bed reactor.
The invention provides a fluorine-removing fixed bed reactor, wherein a solid filler in the fluorine-removing fixed bed reactor is a porous ceramic material prepared by the porous ceramic material or the preparation method in the technical scheme.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 2500g of cerium lanthanum carbonate, 100g of aluminum oxide and 100g of silicon dioxide, mixing and stirring the materials in a stirrer for 20min, uniformly mixing the materials, pre-sintering the materials in a muffle furnace at the pre-roasting temperature of 800 ℃ for 2h, grinding the materials by a Raymond mill after roasting, and sieving the materials by a 100-mesh sieve to obtain precursor powder; weighing 2000g of precursor powder, 250g of calcium carbonate and 200g of epoxy resin, uniformly mixing to obtain a well-mixed premix, wherein the solid-liquid ratio is 2:1 (mass ratio) is added into a water stirrer and stirred for 10min to obtain a pasty raw material, spherical particles with the particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm are prepared by a ball making machine, 200g of spherical particles with the particle diameters of 1-10 mm are prepared in each specification, the spherical particles are put into a muffle furnace for sintering, the muffle furnace is heated linearly to 300 ℃ from room temperature according to 20 ℃/min, then is heated for 1.5h, and is heated to 1300 ℃ according to 10 ℃/min for sintering for 4h to obtain porous ceramic particles.
Application example 1
Selecting 5 hollow glass cylinders with the diameter of 10cm and the height of 50cm, and numbering 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 in the order of the particle size from small to large, and filling the porous ceramic particles from low to high, paving the ceramic particles with the particle size of 10 in each glass cylinder in the thickness of 5cm, connecting the bottom of the No. 1 column with the top of the No. 2 column by using a hose, and connecting the two columns by analogy, taking 1000mL of rare earth feed liquid with the concentration of 150g/L, pumping the feed liquid from the top of the No. 1 column by using a peristaltic pump at the concentration of 100mL/min, and sequentially passing through the No. 1-5 cylinders. The initial feed liquid contains 2.8g/L of fluorine, and the initial feed liquid contains 1g/L of fluorine after passing through a No. 1 column; passing through a No. 2 column, the fluorine-containing concentration is 0.4g/L; passing through a No. 3 column, the fluorine-containing concentration is 0.09g/L; passing through a No. 4 column, the fluorine-containing concentration is 0.04g/L; after 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 types of rare earth elements in the feed liquid and the percentage (wt%) of various rare earth raw materials in the total amount of the rare earth elements in the application example are shown in table 1.
TABLE 1 composition of rare earths in the feed liquid
Figure BDA0003766946440000081
Example 2
Taking 2000g of lanthanum cerium carbonate, 350g of aluminum oxide and 350g of silicon dioxide, mixing and stirring the materials in a stirrer for 20min, uniformly mixing, pre-sintering in a muffle furnace at the pre-roasting temperature of 900 ℃ for 4h, grinding the materials by a Raymond mill after roasting, and sieving the materials by a 100-mesh sieve to obtain precursor powder; weighing 2000g of precursor powder and 200g of calcium carbonate 100g of epoxy resin, uniformly mixing to obtain a well-mixed premix, wherein the solid-liquid ratio is 3:1 (mass ratio) is added into a water stirrer and stirred for 10min to obtain a pasty raw material, spherical particles with the particle sizes of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm are prepared by a ball making machine, 200g of spherical particles with the particle sizes of 1-10 mm are prepared in each specification, the spherical particles are put into a muffle furnace for sintering, the muffle furnace is heated linearly to 300 ℃ from room temperature according to 5 ℃/min, then is heated for 1.5h, and is heated to 1400 ℃ according to 15 ℃/min for sintering for 4h to obtain porous ceramic particles.
Application example 2
Selecting 5 hollow glass cylinders with the diameter of 10cm and the height of 50cm, and numbering 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 in the order of the particle size from small to large, and filling the porous ceramic particles from low to high, paving the ceramic particles with the particle size of 10 in each glass cylinder in the thickness of 5cm, connecting the bottom of the No. 1 column with the top of the No. 2 column by using a hose, and connecting the two columns by analogy, taking 1000mL of rare earth feed liquid with the concentration of 150g/L, pumping the feed liquid from the top of the No. 1 column by using a peristaltic pump with the concentration of 150mL/min, and sequentially passing through the No. 1-5 cylinders. The initial feed liquid contains 2.8g/L of fluorine, and the fluorine concentration is 1.5g/L after passing through a No. 1 column; passing through a No. 2 column, the fluorine-containing concentration is 0.8g/L; passing through a No. 3 column, the fluorine-containing concentration is 0.3g/L; passing through a No. 4 column, the fluorine-containing concentration is 0.08g/L; passing through a No. 5 column, the fluorine-containing concentration is 0.05g/L, and the final rare earth concentration of the feed liquid is 148g/L. The types of rare earth elements in the feed liquid and the percentage (wt%) of various rare earth raw materials in the total amount of the rare earth elements in the 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 the materials in a stirrer for 20min, uniformly mixing the materials, pre-sintering the materials in a muffle furnace at the pre-roasting temperature of 1000 ℃ for 2h, grinding the materials by a Raymond mill after roasting, and sieving the materials by a 100-mesh sieve to obtain precursor powder; weighing 2000g of precursor powder and 200g of calcium carbonate 250g of epoxy resin, uniformly mixing to obtain a well-mixed premix, wherein the solid-liquid ratio is 4:1 (mass ratio) is added into a water stirrer and stirred for 10min to obtain a pasty raw material, spherical particles with the particle diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm and 10mm are prepared by a ball making machine, 200g of the spherical particles with the particle diameters of 1-10 mm are prepared according to each specification, the spherical particles are placed into a muffle furnace for sintering, the muffle furnace linearly heats up to 300 ℃ from room temperature according to 10 ℃/min, then keeps the temperature for 1.5h, and heats up to 1500 ℃ according to 20 ℃/min for sintering for 6h to obtain the porous ceramic particles. The types of rare earth elements in the feed liquid and the percentage (wt%) of various rare earth raw materials in the total amount of the rare earth elements in the 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 numbering 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 in the order of the particle size from small to large, and filling the porous ceramic particles from low to high, paving the ceramic particles with the particle size of 10 in each glass cylinder in the thickness of 5cm, connecting the bottom of the No. 1 column with the top of the No. 2 column by using a hose, and connecting the two columns by analogy, taking 1000mL of rare earth feed liquid with the concentration of 150g/L, pumping the feed liquid from the top of the No. 1 column by using a peristaltic pump at the concentration of 100mL/min, and sequentially passing through the No. 1-5 cylinders. The initial feed liquid contains 2.8g/L of fluorine, and the initial feed liquid passes through a No. 1 column, and the concentration of the fluorine is 0.8g/L; passing through a No. 2 column, the fluorine-containing concentration is 0.1g/L; passing through a No. 3 column, the fluorine-containing concentration is 0.03g/L; passing through a No. 4 column, the fluorine-containing concentration is 0.03g/L; after 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 types of rare earth elements in the feed liquid and the percentage (wt%) of various rare earth raw materials in the total amount of the rare earth elements in the application example are shown in table 1.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. The porous ceramic material is characterized in that the preparation raw materials comprise the following components in percentage by mass:
48 to 88.2 percent of cerium lanthanum 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.
2. The porous ceramic material according to claim 1, wherein the particle size of the porous ceramic material is 1 to 10mm.
3. A process for the preparation of a porous ceramic material according to claim 1 or 2, characterized in that it comprises the following steps:
wet mixing the preparation raw materials with water to obtain granulation materials;
granulating the granulated material to obtain a granulated material;
and sintering the granules to obtain the porous ceramic material.
4. The production method according to claim 3, wherein 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.
5. The production method according to claim 4, wherein a temperature rising rate from room temperature to the temperature of the first sintering and a temperature rising rate from the temperature of the first sintering to the temperature of the second sintering are independently 5 to 20 ℃/min.
6. The method of claim 3, further comprising, prior to the wet mixing, pre-treating the preparation feedstock; the pretreatment comprises the following steps:
mixing lanthanum cerium carbonate, aluminum oxide and silicon dioxide, and then pre-sintering 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 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.
7. The production method according to claim 3 or 6, wherein the mass ratio of the production raw material to water is (2-4): 1.
8. Use of the porous ceramic material according to claim 1 or 2 or prepared by the preparation method according to any one of claims 3 to 7 for the removal of fluoride ions.
9. The application according to claim 8, wherein the application is: obtaining a fixed bed reactor by using the porous ceramic material as a solid filler; and (3) flowing the liquid containing the fluoride ions through the fixed bed reactor to remove the fluoride ions.
10. A fluorine-removing fixed bed reactor, characterized in that the solid filler in the fluorine-removing fixed bed reactor is 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 to 7.
CN202210889522.6A 2022-07-27 2022-07-27 Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal Active CN115228451B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210889522.6A CN115228451B (en) 2022-07-27 2022-07-27 Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210889522.6A CN115228451B (en) 2022-07-27 2022-07-27 Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal

Publications (2)

Publication Number Publication Date
CN115228451A true CN115228451A (en) 2022-10-25
CN115228451B CN115228451B (en) 2023-08-15

Family

ID=83675699

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210889522.6A Active CN115228451B (en) 2022-07-27 2022-07-27 Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal

Country Status (1)

Country Link
CN (1) CN115228451B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102701723A (en) * 2012-06-21 2012-10-03 上海大学 Preparation method of Ce-doped LaAlO3 flickering ceramic material
CN103979937A (en) * 2014-05-19 2014-08-13 河北工业大学 Iron tailing far-infrared ceramic material containing rare earth and method for preparing iron tailing far-infrared ceramic material
JP2014227324A (en) * 2013-05-23 2014-12-08 宮川化成工業株式会社 Porous ceramics sintered body and method for producing the same
CN105126738A (en) * 2015-08-08 2015-12-09 常州大学 Preparation method of porous composite material for removal of fluorine ions from water
CN111825475A (en) * 2019-04-22 2020-10-27 内蒙古科技大学 Modified red mud porous ceramic and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102701723A (en) * 2012-06-21 2012-10-03 上海大学 Preparation method of Ce-doped LaAlO3 flickering ceramic material
JP2014227324A (en) * 2013-05-23 2014-12-08 宮川化成工業株式会社 Porous ceramics sintered body and method for producing the same
CN103979937A (en) * 2014-05-19 2014-08-13 河北工业大学 Iron tailing far-infrared ceramic material containing rare earth and method for preparing iron tailing far-infrared ceramic material
CN105126738A (en) * 2015-08-08 2015-12-09 常州大学 Preparation method of porous composite material for removal of fluorine ions from water
CN111825475A (en) * 2019-04-22 2020-10-27 内蒙古科技大学 Modified red mud porous ceramic and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
SHI QIANTAO ET AL.: "Synthesis, characterization and application of lanthanum-impregnated activated alumina for F removal", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
唐伟博;江嘉翔;肖治国;钟海伦;成岳;: "铈改性多孔陶粒处理高氟地下(表)水的试验研究", 环保科技 *
王杰;麻永林;杨艳茹;邢淑清;: "稀土镧负载粉煤灰多孔陶粒的制备和应用", 内蒙古科技大学学报 *
石稳民;付有为;许智;罗春光;李道圣;康建雄;: "镧负载多孔陶粒用于低浓度含磷废水的处理", 环境科学与技术 *

Also Published As

Publication number Publication date
CN115228451B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
AU2011247702B2 (en) Method for preparing metallurgical-grade alumina by using fluidized bed fly ash
KR102008582B1 (en) A Method for Preparing Nickel-Cobalt-Manganese Complex Sulfate Solution by Recycling A Waste Cathode Material of Lithium Secondary Battery Using Solvent Extraction Process to Control Impurities
CN111072071B (en) Method for producing polymeric aluminum ferric sulfate water purifying agent and silica gel by using iron tailings
CN111842411B (en) Red mud full-recycling method
CN105585039B (en) Efficient and rapid desiliconization method for bauxite
CN107879367A (en) A kind of red mud Comprehensive utilization method
CN103088205B (en) Beryllium oxide production process
CN113462899A (en) Rare earth recovery method with high recovery rate
CN109338113A (en) A kind of method of Ca- chloride vat blue RS technology recycling neodymium iron boron sets of holes greasy filth waste material
CN104150570A (en) Method for extracting chromium from chromium-containing waste liquor
CN115228451A (en) Porous ceramic material, preparation method thereof and application thereof in fluoride ion removal
CN101851000A (en) Method for preparing rare-earth oxide
CN105886772B (en) Comprehensive recycling method of waste rare earth type Y molecular sieve catalyst
CN105296763B (en) Method for separating and recovering cobalt and manganese in low-cobalt high-manganese waste by using ammonia-ammonium carbonate
CN105349790B (en) Method for separating and recovering cobalt and manganese in low-cobalt high-manganese waste by using ammonia-ammonium bicarbonate
CN111560529A (en) Method for recovering germanium from germanium-containing material
CN106916949B (en) The technique of P204 extractions Extraction of rare earth from southern RE ore
CN103225023A (en) Method for leaching and recovering rare earth element from rare earth slag
CN109607914A (en) A kind of technique for treating industrial wastewater of rare metal
EP3342886B1 (en) Useful method for separating light rare earth elements and heavy rare earth elements
CN102115143A (en) Method for producing calcium sulfate from carbide slag
CN103773953A (en) Method for gathering eluate with low rare earth concentration by adopting ionic exchange method
KR20190109082A (en) Recovery method rare earth elements from waste RE:YAG crystal
CN115608519A (en) Calcium-method vanadium extraction tailings flotation desulfurization collecting agent and preparation method thereof
CN102060976B (en) Method for preparing epoxy toughening diluent from solar silicon wafer cutting waste liquid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant