CN112624191A - Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition - Google Patents
Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition Download PDFInfo
- Publication number
- CN112624191A CN112624191A CN202011022938.5A CN202011022938A CN112624191A CN 112624191 A CN112624191 A CN 112624191A CN 202011022938 A CN202011022938 A CN 202011022938A CN 112624191 A CN112624191 A CN 112624191A
- Authority
- CN
- China
- Prior art keywords
- tetragonal
- nano zirconia
- precursor
- zirconia
- temperature
- 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.)
- Pending
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002243 precursor Substances 0.000 title claims abstract description 33
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004615 ingredient Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000411 inducer Substances 0.000 claims abstract description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- -1 zirconium ions Chemical class 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 34
- 239000000047 product Substances 0.000 abstract description 17
- 239000011780 sodium chloride Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 17
- 239000012452 mother liquor Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/22—Preparation in the form of granules, pieces, or other shaped products
- C01D3/24—Influencing the crystallisation process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a precursor ingredient for preparing tetragonal nano zirconia, which is prepared by mixing a tetragonal nano zirconia raw material, a crystal form inducer and water and controlling the pH value of a precursor liquid to be 9.0-10.0. Meanwhile, the invention also discloses a method for producing the tetragonal nano zirconia under the low-temperature condition suitable for the precursor ingredients. The method can directly prepare the tetragonal superfine zirconia under the low-temperature reaction condition without high-energy-consumption working procedures such as high-temperature sintering, gas crushing and the like; the drying and granulating process is completed in one step through the spray granulating process, and the product is zirconia powder with high sphericity; the raw materials do not need a high-precision impurity removal process, and a zirconium oxide product with qualified purity can be prepared; ammonia water is not adopted in the preparation process, and the only byproduct sodium chloride is sold as industrial salt, so that the process system is an energy-saving, green and environment-friendly industrial production technology.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a precursor ingredient for preparing tetragonal nano zirconia and a method for producing the tetragonal nano zirconia at low temperature by adopting the ingredient.
Background
Zirconium dioxide is an important structural and functional material, and has very excellent physical and chemical properties, such as high melting point (2700 ℃) and boiling point, small thermal conductivity, large thermal expansion coefficient, high temperature resistance, good wear resistance, excellent corrosion resistance and the like. Nanometer level zirconium dioxide material has some unique performance, such as insulator at normal temperature and conductivity, sensitivity, toughness, etc. at high temperature, and thus has important use. It has wide applications in many different fields, such as ceramic pigments, engineering ceramics, gem industry, piezoelectric elements, ion exchangers, and solid electrolytes. Zirconium dioxide is also the only metal oxide with acidity, alkalinity, oxidizability and reducibility, and it is a type-I p-type semiconductor, which is easy to generate oxygen cavity as catalyst carrier and can interact with active component, therefore, the catalyst using zirconium dioxide as carrier shows considerable application prospect and important theoretical research value.
Zirconium dioxide has three crystal structures: monoclinic (m-ZrO 2), tetragonal (t-ZrO 2) and cubic (c-ZrO 2) phase transformation conditions were as follows:
the lattice parameters of zirconia are as follows:
the main fields of application of zirconium dioxide are as follows:
TABLE 1 field of application of zirconium dioxide
The production process of the conventional high-purity superfine zirconia comprises the following steps:
heating industrial zirconium oxychloride in dilute hydrochloric acid to dissolve, adding proper quantity of edible gelatin solution to remove silicon dioxide, fine filtering, making three-time recrystallization, making spectral analysis, and using ultrapure water to prepare the invented productZrOCl with certain concentration2And (3) solution. Washing industrial liquid ammonia with 1% potassium permanganate aqueous solution, 2% sodium hydroxide aqueous solution and ultrapure water, strictly controlling flow rate, absorbing with ultrapure water, and obtaining high-purity ammonia water by spectral analysis when the concentration of ammonia water reaches 28%. Under the condition of violent stirring in a nonmetal container, injecting calculated amounts of ammonia water and zirconium hydroxide solution until the pH is 8-8.5, and repeatedly washing with ultrapure water until no Cl exists-Until 250 to 300 ℃ after centrifugal separationoC, drying, and then drying in 850-1100oAnd C, firing at a high temperature to obtain the high-purity superfine zirconia (specifically shown in figure 1). Zirconium oxide
The conventional preparation process of the high-purity superfine zirconia product adopts a high-temperature sintering mode for crystallization, so that raw materials must be strictly purified, a precursor prepared by a precipitation reaction is mostly an amorphous product, the specific surface area is large, a large amount of impurity ions are easily adsorbed, a large amount of washing water is needed for washing, otherwise, non-volatile impurities are remained in or on the zirconia crystal in the sintering process, and the purity of the product is influenced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a precursor ingredient for preparing square nano zirconia aiming at the defects of the prior art.
The invention also aims to provide a method for producing the tetragonal nanometer zirconia at low temperature by adopting the precursor ingredients.
The technical scheme is as follows: in order to achieve the above object, the present invention is specifically as follows: a precursor ingredient for preparing square nano zirconia is characterized in that a square nano zirconia raw material, a crystal form inducer and water are mixed, and the pH value of a precursor material liquid is controlled to be 9.0-10.0.
Wherein, the crystal form inducer is one or the combination of alcohols or amine solvents with lone pair electrons in molecules.
Wherein the mixing addition molar ratio of the tetragonal nano zirconia to the crystal form inducer is 1: 0.5-1: 2.0; the adding amount of the water is preferably controlled to control the molar concentration of zirconium ions in the precursor liquid to be 0.02-1.0 mol/L.
Wherein, the crystal form inducer is one or a combination of more of ethylene glycol, glycerol, isopropanol, ethanolamine, triethanolamine and propanolamine.
The method for producing the tetragonal nanometer zirconia by using the precursor ingredients under the low-temperature condition comprises the following steps:
(1) mixing a tetragonal nano zirconia raw material, a crystal form inducer and ultrapure water into a precursor feed liquid, and then adding liquid caustic soda to control the pH value to be 9.0-10.0;
(2) crystallizing the precursor liquid obtained in the step (1) by adopting a hydrothermal reaction mode to obtain zirconium oxide crystal slurry;
(3) washing the zirconium oxide crystal slurry obtained in the step (2) with ultrapure water until the content of chloride ions is less than or equal to 50ppm, and obtaining zirconium oxide wet crystal slurry;
(4) and (4) preparing the wet crystal slurry of zirconium oxide obtained in the step (3) into slurry liquid for spray granulation, and then drying the slurry liquid in a spray drying system to obtain a finished product.
Wherein, the hydrothermal reaction process in the step (2) comprises heating, constant-temperature curing and cooling in the hydrothermal reaction crystallization process; the temperature rise process is to slowly rise the temperature to 60-80 DEG CoC, the temperature rise rate is 4-6oC/h, then quickly heating to 180-200 DEG CoC, the heating rate is 30-90oC/h; the constant-temperature curing process is 180-200%oC, curing at constant temperature for 2-12 h.
And (3) wherein the device suitable for the temperature reduction process in the hydrothermal reaction process in the step (2) is a high temperature reduction device and comprises one or more combinations of a high-efficiency wound heat exchanger and a plate heat exchanger.
Wherein the mass ratio of the wet crystal slurry of zirconium oxide to the solvent water, the dispersant and the binder in the slurry liquid for spray granulation is 1: 0.05-0.2: 0.02-0.05: 0.01 to 0.03. The dispersant is one or more of ethanol, fatty acid, glycerol and glycol; the binder is one or a combination of more of starch, dextrin, polyvinyl alcohol and carboxymethyl cellulose.
The method for producing the tetragonal nanometer zirconia under the low temperature condition mainly comprises the processes of precursor material preparation, hydrothermal reaction crystallization, solid-liquid separation and washing, spray drying and sodium chloride byproduct recovery.
The device for completing the solid-liquid separation and washing process can be selected from one or a combination of a self-rotating ceramic membrane, a tubular centrifuge and a disc centrifuge, and the amount of washing water is 4-6 times of the mass of a zirconia product.
Wherein, the atomizing nozzle in the device for completing the spray drying process is one or the combination of two fluids and a high-speed centrifugal type, the pressure of compressed air is 0.3-0.7 MPa, the gas-liquid mass ratio of the compressed air to the crystal slurry is 5: 1-10: 1, and the temperature of a hot air inlet is 210-260%oC, preferably 105 to 120oC。
Wherein, the system for completing the recovery process of the sodium chloride byproduct comprises sodium chloride evaporative crystallization, solid-liquid separation, steam condensate water and recycling of residual mother liquor; the solid-liquid separation equipment is one or two combination of a double-stage piston pusher centrifuge and a horizontal spiral filtering centrifuge. The evaporation crystallization temperature is 80-90 DEG CoC。
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the tetragonal superfine zirconia can be directly prepared under the low-temperature reaction condition, and high-energy-consumption procedures such as high-temperature sintering, gas crushing and the like are not needed;
(2) the drying and granulating process is completed in one step through the spray granulating process, and the product is zirconia powder with high sphericity;
(3) the raw materials do not need a high-precision impurity removal process, and a zirconium oxide product with qualified purity can be prepared;
(4) the ammonia-free process is adopted, and the only byproduct sodium chloride is sold as industrial salt, so that the process system is an energy-saving, green and environment-friendly industrial production technology.
Drawings
FIG. 1 is a flow chart of the conventional high-temperature gel method for producing high-purity superfine zirconia.
FIG. 2 is a schematic process diagram of the system of the present invention.
FIG. 3 is a photograph of a crystal of tetragonal zirconia of example 1.
Figure 4 is a crystal XRD pattern of tetragonal zirconia of example 1.
Detailed Description
Example 1:
fig. 1 shows that a tetragonal nano zirconia industrial production system suitable for the process comprises: a dissolution, precursor dosing system; a hydrothermal reaction crystallization system; a solid-liquid separation and washing system; a spray drying system; sodium chloride evaporative crystallization system.
(1) Dissolving and precursor compounding: dissolving ZrOCl2 & 8H2O and solvent (ultrapure water for the first time, residual mother liquor of sodium chloride evaporative crystallization, steam condensate and make-up water) in a dissolving tank to prepare the ZrOCl in the solution2The content reaches 21.5 percent, and the dissolution temperature is 20 ℃. Dripping crystal form inducer with the addition amount ratio of [ Zr4+]: [ Crystal form inducer]=1:1.0 (molar ratio). Adding a proper amount of bottom water into a precursor preparation reaction kettle, starting stirring, and simultaneously dropwise adding ZrOCl2The pH of the feed liquid is controlled to be 9.5.
(2) Hydrothermal reaction crystallization process: transferring the prepared precursor liquid into a hydrothermal reaction crystallizer, sealing, starting stirring, and slowly heating to 70 deg.CoC, the temperature rising rate is 5oC/h, and then the temperature rises to 180 ℃ rapidlyoC, the heating rate is 60oAnd C/h and 180 ℃ constant-temperature curing is carried out for 10h, after the reaction is finished, the zirconium oxide crystal slurry is cooled through a high-efficiency winding type heat exchanger, the zirconium oxide crystal slurry is conveyed to a crystal slurry buffer tank, a crystal photo is shown in figure 2, and the XRD diffraction of the crystal is shown in figure 3.
(3) Solid-liquid separation and washing: and (3) carrying out solid-liquid separation and continuous washing processes by adopting a rotary ceramic membrane, wherein the consumption of washing water is 5.5 times of that of the zirconia product, and the content of chloride ions in the washing separation mother liquor is detected to be less than or equal to 50 ppm.
(4) Spray drying: mixing the wet crystal slurry subjected to solid-liquid separation with solvent water, a dispersing agent and a binder according to a mass ratio of 1: 0.15: 0.05:0.02, conveying the slurry to a spray drying system by a screw conveying pump, adopting a two-fluid atomization nozzle, controlling the gas-liquid ratio of the flow of compressed air to the flow of crystal slurry to be 7:1, and controlling the pressure of the compressed air0.4MPa, hot air inlet temperature of 250oC, hot air outlet temperature 105oAnd C, conveying the dried product to a product bin through a caking air flow, and packaging the finished product.
(5) Sodium chloride evaporative crystallization system: the residual mother liquor and washing water after solid-liquid separation enter a sodium chloride continuous evaporation crystallization system together to crystallize and separate out sodium chloride crystals with uniform granularity, and the evaporation crystallization temperature is 85 DEGoAnd C, the purity of the sodium chloride reaches 98.23%, and the steam condensate and the evaporation mother liquor residual liquid return to the dissolving and batching process.
Example 2:
another tetragonal nano zirconia industrial production system suitable for the process as shown in fig. 1 comprises: a dissolution, precursor dosing system; a hydrothermal reaction crystallization system; a solid-liquid separation and washing system; a spray drying system; sodium chloride evaporative crystallization system.
(1) Dissolving and precursor compounding: taking ZrOCl2·8H2Dissolving and proportioning O and a solvent (ultrapure water for the first time, residual mother liquor of sodium chloride evaporative crystallization, steam condensate and make-up water for the later time) in a dissolving tank to ensure that ZrOCl in the solution2The content reaches 16.5 percent, and the dissolving temperature is 25 percentoC. Dripping crystal form inducer with the addition amount ratio of [ Zr4+]: [ Crystal form inducer]=1:0.8 (molar ratio). Adding a proper amount of bottom water into a precursor preparation reaction kettle, starting stirring, and simultaneously dropwise adding ZrOCl2The pH of the feed liquid is controlled to be 10.0.
(2) Hydrothermal reaction crystallization process: transferring the prepared precursor liquid into a hydrothermal reaction crystallizer, sealing, starting stirring, and slowly heating to 60 deg.CoC, the heating rate is 4oC/h, then quickly heating to 190oC, the heating rate is 50oC/h，190oC, curing at constant temperature for 8h, cooling through a high-efficiency wound heat exchanger after the reaction is finished, and conveying the zirconium oxide crystal slurry to a crystal slurry buffer tank.
(3) Solid-liquid separation and washing: and (3) carrying out solid-liquid separation and continuous washing processes by adopting a rotary ceramic membrane, wherein the consumption of washing water is 5 times of that of the zirconia product, and the content of chloride ions in the washing separation mother liquor is detected to be less than or equal to 50 ppm.
(4) Spray drying: mixing the wet crystal slurry subjected to solid-liquid separation with solvent water, a dispersing agent and a binder according to a mass ratio of 1: 0.1: 0.04: 0.03, conveying the slurry to a spray drying system by a screw rod conveying pump, adopting a two-fluid atomization nozzle, wherein the gas-liquid ratio of the flow of compressed air to the flow of crystal slurry is 8:1, the pressure of the compressed air is 0.5MPa, and the temperature of a hot air inlet is 230oC, hot air outlet temperature 110oAnd C, conveying the dried product to a product bin through a caking air flow, and packaging the finished product.
(5) Sodium chloride evaporative crystallization system: the residual mother liquor and washing water after solid-liquid separation enter a sodium chloride continuous evaporation crystallization system together to crystallize and separate out sodium chloride crystals with uniform granularity, and the evaporation crystallization temperature is 80 DEGoAnd C, the purity of the sodium chloride reaches 98.63 percent, and the steam condensate and the evaporation mother liquor residual liquid return to the dissolving and proportioning process.
Claims (9)
1. A precursor ingredient for preparing square nano zirconia is characterized in that a square nano zirconia raw material, a crystal form inducer and water are mixed, and the pH value of a precursor material liquid is controlled to be 9.0-10.0.
2. The precursor ingredient for preparing the tetragonal nano zirconia according to claim 1, wherein the crystal form inducer is one or a combination of alcohol or amine solvents with lone pair electrons in the molecule.
3. The precursor ingredient for preparing the tetragonal nano zirconia according to claim 1, wherein the molar ratio of the tetragonal nano zirconia to the crystal form inducer is 1: 0.5-1: 2.0; the adding amount of the water is controlled to control the molar concentration of zirconium ions in the precursor liquid to be 0.02-1.0 mol/L.
4. The precursor ingredient for preparing the tetragonal nano zirconia according to claim 1, wherein the crystal form inducer is one or more of ethylene glycol, glycerol, isopropanol, ethanolamine, triethanolamine and propanolamine.
5. The method for producing tetragonal nano zirconia by using the precursor ingredients in any one of claims 1 to 4 under the low-temperature condition is characterized by comprising the following steps:
(1) mixing a tetragonal nano zirconia raw material, a crystal form inducer and ultrapure water into a precursor feed liquid, and then adding liquid caustic soda to control the pH value to be 9.0-10.0;
(2) crystallizing the precursor liquid obtained in the step (1) by adopting a hydrothermal reaction mode to obtain zirconium oxide crystal slurry;
(3) washing the zirconium oxide crystal slurry obtained in the step (2) with ultrapure water until the content of chloride ions is less than or equal to 50ppm, and obtaining zirconium oxide wet crystal slurry;
(4) and (4) preparing the wet crystal slurry of zirconium oxide obtained in the step (3) into slurry liquid for spray granulation, and then drying the slurry liquid in a spray drying system to obtain a finished product.
6. The method for producing tetragonal nano zirconia at low temperature according to claim 5, wherein the hydrothermal reaction process in the step (2) comprises heating, constant temperature aging and cooling of a hydrothermal reaction crystallization process; the temperature rise process is to slowly rise the temperature to 60-80 DEG CoC, the temperature rise rate is 4-6oC/h, then quickly heating to 180-200 DEG CoC, the heating rate is 30-90oC/h; the constant-temperature curing process is 180-200%oC, curing at constant temperature for 2-12 h.
7. The method for producing tetragonal nanometer zirconia at low temperature according to claim 6, wherein the device suitable for the temperature reduction process in the hydrothermal reaction process in the step (2) is a high temperature reduction device, and the device comprises one or more of a high-efficiency wound heat exchanger and a plate heat exchanger.
8. The method for producing the tetragonal nanometer zirconia under the low temperature condition according to claim 5, wherein the mass ratio of the wet zirconia crystal slurry to the solvent water, the dispersant and the binder in the slurry liquid for spray granulation is 1: 0.05-0.2: 0.02-0.05: 0.01 to 0.03.
9. The method for producing tetragonal nano zirconia under the low temperature condition according to claim 8, wherein the dispersant is one or more of ethanol, fatty acid, glycerol and glycol; the binder is one or a combination of more of starch, dextrin, polyvinyl alcohol and carboxymethyl cellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011022938.5A CN112624191A (en) | 2020-09-25 | 2020-09-25 | Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011022938.5A CN112624191A (en) | 2020-09-25 | 2020-09-25 | Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112624191A true CN112624191A (en) | 2021-04-09 |
Family
ID=75302711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011022938.5A Pending CN112624191A (en) | 2020-09-25 | 2020-09-25 | Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112624191A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190951A (en) * | 2018-03-07 | 2018-06-22 | 济南大学 | A kind of hydro-thermal method regulates and controls nano zirconium dioxide crystallite dimension and the method for crystal form simultaneously |
| CN109467431A (en) * | 2018-11-20 | 2019-03-15 | 江西省钨与稀土产品质量监督检验中心（江西省钨与稀土研究院） | A kind of yttrium stablizes cubic phase nano zirconium oxide and preparation method thereof |
| CN109574073A (en) * | 2018-06-13 | 2019-04-05 | 上海上惠纳米科技有限公司 | A kind of preparation method of high dispersion nanometer oxide zirconium powder |
| CN110203969A (en) * | 2019-06-28 | 2019-09-06 | 河南科技大学 | A kind of high dispersive cubic phase nano zirconium oxide and preparation method thereof |
-
2020
- 2020-09-25 CN CN202011022938.5A patent/CN112624191A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190951A (en) * | 2018-03-07 | 2018-06-22 | 济南大学 | A kind of hydro-thermal method regulates and controls nano zirconium dioxide crystallite dimension and the method for crystal form simultaneously |
| CN109574073A (en) * | 2018-06-13 | 2019-04-05 | 上海上惠纳米科技有限公司 | A kind of preparation method of high dispersion nanometer oxide zirconium powder |
| CN109467431A (en) * | 2018-11-20 | 2019-03-15 | 江西省钨与稀土产品质量监督检验中心（江西省钨与稀土研究院） | A kind of yttrium stablizes cubic phase nano zirconium oxide and preparation method thereof |
| CN110203969A (en) * | 2019-06-28 | 2019-09-06 | 河南科技大学 | A kind of high dispersive cubic phase nano zirconium oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高龙柱: "纳米氧化锆制备及晶型控制的水热法研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110668452B (en) | Preparation of SiO from fly ash2-Al2O3Method of compounding aerogel materials | |
| CN104477978B (en) | A kind of method preparing perovskite nano-powder | |
| CN111153434A (en) | Preparation method of lanthanum zirconate spherical powder for thermal spraying | |
| NO872913L (en) | PREPARATION OF UNAGGLOMATED PARTICLES OF METAL OXYDE WITH UNIFORM PARTICLE IRRIGATION. | |
| CN106866142A (en) | The production method of nanoscale high-purity zirconium dioxide composite granule | |
| CN105645959B (en) | Y2O3The spraying codepostion preparation method of base transparent ceramic powder | |
| CN104003697A (en) | Preparation method of BSAS composite ceramic powder | |
| CN105366718A (en) | Nanometer zirconia powder and synthesis method thereof | |
| CN102369161A (en) | Method for producing alkali metal niobate particles, and alkali metal niobate particles | |
| JP2005255450A (en) | Zirconium oxide crystal particle and method for producing the same | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN102718258A (en) | Preparation method of Gd2Zr2O7 nano-powder | |
| CN101708861B (en) | Method for preparing barium titanate | |
| CN105502480B (en) | Hydrangea-like strontium titanate nano powder preparation method | |
| CN103601210B (en) | Wilkinite one step alkali is fused into the method for zeolite | |
| CN100465096C (en) | Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material | |
| CN1032585C (en) | Preparation for super fine powder of titanium dioxide | |
| CN106745120A (en) | It is a kind of prepare three-dimensional flower-shaped boehmite without the hot method of template mixed solvent | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material | |
| CN108609652A (en) | A method of preparing Zirconium dioxide nano powder using fused salt | |
| CN101497524A (en) | Preparation of compact magnesia partial stabilized zirconia ceramic | |
| CN112624191A (en) | Precursor ingredient for preparing tetragonal nano zirconia and method for producing tetragonal nano zirconia under low temperature condition | |
| CN103011278B (en) | Process for hydrothermally preparing zirconium oxychloride with low alkali consumption | |
| CN103101975B (en) | Rodlike bismuth oxide and preparation method thereof | |
| CN104071844A (en) | Burning method for preparing Sr2YTaO6 powder |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210409 |
|
| RJ01 | Rejection of invention patent application after publication |