CN114735730B - High-purity zinc aluminate spinel and preparation method thereof - Google Patents
High-purity zinc aluminate spinel and preparation method thereof Download PDFInfo
- Publication number
- CN114735730B CN114735730B CN202210223631.4A CN202210223631A CN114735730B CN 114735730 B CN114735730 B CN 114735730B CN 202210223631 A CN202210223631 A CN 202210223631A CN 114735730 B CN114735730 B CN 114735730B
- Authority
- CN
- China
- Prior art keywords
- zinc
- mixed solution
- aqueous solution
- aluminum
- purity
- 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.)
- Active
Links
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 118
- 239000011029 spinel Substances 0.000 title claims abstract description 118
- 239000011701 zinc Substances 0.000 title claims abstract description 73
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 60
- -1 zinc aluminate Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 85
- 239000011259 mixed solution Substances 0.000 claims abstract description 85
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000007864 aqueous solution Substances 0.000 claims abstract description 60
- 239000011734 sodium Substances 0.000 claims abstract description 46
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 150000003751 zinc Chemical class 0.000 claims abstract description 34
- 230000032683 aging Effects 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000004448 titration Methods 0.000 claims abstract description 24
- 230000003068 static effect Effects 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 29
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 239000012535 impurity Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 10
- 230000002572 peristaltic effect Effects 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052566 spinel group Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000283899 Gazella Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NJZCXJFFBAXISR-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-].[Al+3] Chemical compound [N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-].[Al+3] NJZCXJFFBAXISR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of zinc-aluminum spinel preparation, in particular to a high-purity zinc-aluminum spinel and a preparation method thereof, wherein the preparation method comprises the following steps: s1, respectively preparing a sodium metaaluminate aqueous solution and a zinc salt aqueous solution according to a proportion; s2, slowly and parallelly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1, controlling the pH value of the mixed solution, and standing and aging the mixed solution after the titration is finished; s3, filtering, washing and drying the mixed solution subjected to static aging in the step S2 to obtain a zinc aluminum spinel precursor; s4, raising the zinc aluminate spinel precursor prepared in the step S4 to a high temperature and roasting at the high temperature to obtain the high-purity zinc aluminate spinel; in the step S2, the molar ratio of the sodium metaaluminate to the zinc salt is 0.5-3. The preparation method provided by the invention reduces the zinc-aluminum ratio, does not introduce extra precipitant, and improves the purity, dispersity and specific surface area of the prepared zinc-aluminum spinel.
Description
Technical Field
The invention relates to the field of zinc-aluminum spinel preparation, in particular to a high-purity zinc-aluminum spinel and a preparation method thereof.
Background
Zinc aluminium spinel (ZnAl) 2 O 4 ) Is AB 2 O 4 Typical spinel-type ternary oxide semiconductors in chemical formulas, zinc ions in tetrahedral planes (a sites), aluminum ions in octahedral planes (B sites),has been considered as a functional material with a plurality of potential application prospects and benefits from ZnAl 2 O 4 The catalyst has the characteristics of high thermal stability, good acid and alkali resistance, high mechanical strength, low acidity, large specific surface area and wide bandgap energy (about 3.8 eV) and the like, can be used as an ultraviolet region activated photoelectron device, such as a sensor and a dielectric material, a ceramic material, an electronic and photoelectric device, a catalyst and a catalyst carrier of transition metal, can be used as a catalyst or a catalyst carrier zinc-aluminum spinel with very high surface energy and crystal boundary energy, can inhibit grain growth, enhance the strong interaction (SMSI) of the metal carrier, improve the dispersibility of active components, increase the thermal stability of the catalyst and improve the catalytic efficiency, and is widely used for the functions of a methanol preparation reaction by carbon dioxide, a high temperature vapor shift reaction (HT-WGS), a carbonylation reaction, a propane oxidation reaction, a reforming hydrogen preparation reaction, a Fischer-Tropsch synthesis reaction, hydrocarbon catalytic combustion, a low carbon alkane dehydrogenation to prepare olefin, a photocatalytic degradation organic pollutant and desulfurization of gasoline and diesel.
The preparation method of the zinc aluminate spinel mainly comprises a solid phase reaction method, a coprecipitation method, a sol-gel method, a hydrothermal synthesis method and the like. However, the solid phase reaction method has high requirements on reaction temperature, low purity of the product, poor uniformity and small specific surface area; the sol-gel method needs to use expensive metal alkoxide, the popularization and the use are limited by the excessive cost, and the prepared zinc-aluminum spinel has poor sintering resistance; the hydrothermal synthesis method has strict requirements on reaction equipment and high operation requirements, and is difficult to popularize in large-scale production, and the prepared zinc aluminum spinel has large crystal grains and poor dispersibility. Compared with the method, the coprecipitation method has simple operation, low requirements on equipment and technology, high product purity and low cost, and is more suitable for large-scale industrial production. The traditional coprecipitation method is to mix a mixed salt solution of zinc salt and aluminum salt, then to drop the mixed salt solution into deionized water with sodium carbonate or sodium hydroxide simultaneously or successively, to precipitate to obtain zinc-aluminum hydrotalcite layered double hydroxide (Zn-Al-LDH), and then to obtain zinc-aluminum spinel by high-temperature roasting. This process requires a relatively high zinc to aluminium ratio, typically 1 by mole<Zn 2+ /Al 3+ <4, but since the molar ratio of zinc to aluminum is much higher than the stoichiometric ratio, zinc oxide, aluminum oxide, for example, will appearThe purity of the zinc aluminate spinel is low, and further acid-base treatment is needed to obtain pure-phase zinc aluminate spinel, so that when the pure-phase zinc aluminate spinel is used as a catalyst for preparing other products, the acid site of the alumina impurity can possibly cause side reactions.
At present, some prior art improves the traditional coprecipitation method to reduce the molar ratio of zinc to aluminum, however, the methods are still the same as the traditional coprecipitation method, carbonate (such as sodium carbonate), urea and the like are required to be introduced as precipitants, the generated zinc-aluminum spinel precursor is double hydroxide (LDH-CO 3) containing carbonate radicals between sheets, the carbonate impurities are harmful in the preparation process (such as polymer additives) of some chemical products, the reduction needs to be controlled as much as possible, and the carbonate impurities release carbon dioxide in the roasting process to increase carbon emission.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art, provides a high-purity zinc-aluminum spinel and a preparation method thereof, reduces the zinc-aluminum ratio, does not introduce extra precipitant, and improves the purity, the dispersity and the specific surface area of the prepared zinc-aluminum spinel.
The technical scheme adopted by the invention is that the preparation method of the high-purity zinc aluminate spinel comprises the following steps:
s1, respectively preparing a sodium metaaluminate aqueous solution and a zinc salt aqueous solution according to a proportion;
s2, slowly and parallelly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1, controlling the pH value of the mixed solution, and standing and aging the mixed solution after the titration is finished;
s3, filtering, washing and drying the mixed solution subjected to static aging in the step S2 to obtain a zinc aluminum spinel precursor;
s4, raising the zinc aluminate spinel precursor prepared in the step S3 to a high temperature and roasting at the high temperature to obtain the high-purity zinc aluminate spinel;
in the step S2, the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-3.
In the technical proposal, the molar ratio of the zinc source to the aluminum source is prepared from the common preparation method1-4 of the method is reduced to 0.5-3, oxide impurities such as zinc oxide and the like in a roasting product are greatly reduced, meanwhile, sodium metaaluminate is used as an aluminum source and a precipitator, metaaluminate and zinc ions can directly react to form a precursor of a zinc-aluminum spinel structure, and the precursor of the zinc-aluminum spinel is generated by coprecipitation after neutralization and aging reaction with zinc salt and is nitrate double hydroxide (Zn-Al-LDH-NO) with low molar ratio of zinc and aluminum 3 ) After coprecipitation roasting, the metaaluminate can be completely combined with zinc ions to form a zinc-aluminum spinel structure, and because no additional precipitants such as common carbonate, urea and the like are added in the coprecipitation process, the zinc-aluminum spinel sheet is free of carbonate-containing double hydroxide (LDH-CO 3 ) Impurities; the method has the advantages that the molar ratio of zinc to aluminum is controlled, the additionally added precipitant is omitted, the purity of the zinc-aluminum spinel is controlled from the molecular level, the generation of oxide impurities and carbon emission during roasting is avoided, the atomic utilization rate and the preparation efficiency are improved to the maximum extent, the roasted product does not need to be further treated, the grain size of the prepared zinc-aluminum spinel is smaller, the purity, the dispersity, the specific surface area and the high-temperature sintering resistance are effectively improved, and the preparation process of downstream chemical products are more environment-friendly.
Further, in step S2, the molar ratio of the zinc salt to sodium metaaluminate is 0.5 to 1.5.
Further, in the step S2, in the slow parallel flow titration process of the sodium metaaluminate aqueous solution and the zinc salt aqueous solution, the mixed solution is heated to 50-90 ℃ while being stirred at the rotating speed of 100-500 r/min, and the temperature is kept; the pH of the mixed solution is controlled to be 5-10; the static aging time of the mixed solution is 20-60 min.
Still further, when the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-0.7, the mixed solution is subjected to complementary titration by using an acidic solution; and when the molar ratio of the zinc salt to the sodium metaaluminate is 0.7-3, using an alkaline solution to supplement titration for the mixed solution.
Still further, the acidic solution is a mixture of one or more of dilute nitric acid, dilute hydrochloric acid, and dilute sulfuric acid, and/or the alkaline solution is a mixture of one or more of sodium hydroxide, sodium carbonate, ammonium bicarbonate, urea, and ammonia water.
Still further, after the mixed solution is subjected to supplementary titration by using one or more of sodium carbonate, ammonium bicarbonate, urea and ammonia water, the acidic solution is dripped to remove impurities.
Preferably, after the mixed solution is subjected to supplementary titration by using one or more of sodium carbonate, ammonium bicarbonate, urea and ammonia water, dilute hydrochloric acid is dripped to remove impurities.
In the technical scheme, when the dosage of sodium metaaluminate is large, the alkalinity of a solution system is strong, so that a small amount of acid solution is needed to control the pH of the system; when the dosage of zinc salt is large, the solution system is biased to be acidic, at the moment, a small amount of alkaline solution except sodium metaaluminate is added to adjust the pH value, the molar ratio of zinc to aluminum in the solution can not be changed, and when the alkaline solution containing carbonate or urea and the like is used, the acidic solution is added subsequently to remove carbonate, so that carbonate impurities are not contained in the zinc-aluminum spinel precursor.
Further, the zinc salt is one or a mixture of more of zinc chloride, zinc nitrate or zinc sulfate.
Further, in the step S3, the washed filter cake is dried at 60-100 ℃ for 8-12 hours.
Further, in the step S4, the zinc aluminate spinel precursor is heated to 400-900 ℃ at a heating rate of 1-3 ℃/min, and then baked for 4.5-10 h.
The invention also provides a high-purity zinc-aluminum spinel, which is prepared by the preparation method of the high-purity zinc-aluminum spinel, and the specific surface area of the high-purity zinc-aluminum spinel is 140-240m 2 ·g -1 The grain diameter is 3-30 nm, the aperture is 2-30 nm, the pore volume is 0.15-0.90 cm 3 /g。
In the technical scheme, sodium metaaluminate and zinc salt are used as raw materials, the mesoporous structure high-purity zinc aluminate spinel is prepared by a coprecipitation method, the specific surface area, the pore diameter and the pore volume of the mesoporous structure high-purity zinc aluminate spinel are larger, the grain size is smaller, the content of oxide impurities in the zinc aluminate spinel is low, carbonate impurities are not contained, the purity of the zinc aluminate spinel is higher, the zinc aluminate spinel is used for catalytic reaction, the catalytic efficiency is higher, and the influence on the application production process can be reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) The zinc-aluminum molar ratio is reduced to be close to the stoichiometric ratio, the content of oxide impurities such as zinc oxide in the prepared zinc-aluminum spinel is reduced, the zinc-aluminum spinel with a mesoporous structure is prepared by directly baking, the preparation method is simple and efficient, the product with high purity can be obtained without further acid-base treatment, the specific surface area, the pore diameter and the pore volume are larger, the grain size is smaller, and the high-temperature sintering resistance is better;
(2) Sodium metaaluminate is used as a raw material and is used as an aluminum source and a precipitator in the preparation process, so that additional precipitants such as carbonate and the like are not required to be added, carbonate impurities are not contained between the prepared zinc-aluminum spinel sheets, the purity of the zinc-aluminum spinel is further improved, and the preparation of a product is not influenced in the application process.
Drawings
FIG. 1 is a scanning electron micrograph of the catalyst of example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the catalyst of example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of the catalyst of example 3 of the present invention.
FIG. 4 is a scanning electron micrograph of the catalyst of comparative example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of the catalyst of comparative example 2 of the present invention.
Detailed Description
The drawings are for illustrative purposes only and are not to be construed as limiting the invention. For better illustration of the following embodiments, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the actual product dimensions; it will be appreciated by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Example 1
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 4.1g NaAlO 2 Respectively dissolving in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in parallel flow at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at the rotation speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, dripping 0.1mol/L dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 2
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 weighing 14.8750g Zn (NO) according to the molar ratio of zinc to aluminum of 1 3 ) 2 ·6H 2 O is dissolved in 200mL deionized water to prepare sodium metaaluminate aqueous solution, and 4.1g NaAlO is weighed 2 Dissolving in 100mL deionized water to prepare zinc nitrate aqueous solution;
s2, feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in parallel flow at a flow rate of 2:1 by using a peristaltic pump, heating the mixed solution to 73 ℃ in a water bath while magnetically stirring at a speed of 300r/min, preserving heat, dripping 0.1mol/L sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 3
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 1.5, 22.3125g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 300mL deionized water to prepare sodium metaaluminate aqueous solution, and 4.1g NaAlO is weighed 2 Dissolving in 100mL deionized water to prepare zinc nitrate aqueous solution;
s2, feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in parallel flow at a flow rate of 3:1 by using a peristaltic pump, heating the mixed solution to 73 ℃ in a water bath while magnetically stirring at a speed of 300r/min, preserving heat, dripping 0.1mol/L sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 4
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 weighing 29.7500g Zn (NO) according to the molar ratio of zinc to aluminum being 2 3 ) 2 ·6H 2 O is dissolved in 400mL of deionized water to prepare a sodium metaaluminate aqueous solution, and 4.1g of NaAlO is weighed 2 Dissolving in 100mL deionized water to prepare zinc nitrate aqueous solution;
s2, feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in parallel flow at a flow rate of 4:1 by using a peristaltic pump, heating the mixed solution to 73 ℃ in a water bath while magnetically stirring at a speed of 300r/min, preserving heat, dripping 0.1mol/L sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 5
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the molar ratio of zinc to aluminum of 2.5, 37.1875g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 500mL deionized water to prepare sodium metaaluminate aqueous solution, and 4.1g NaAlO is weighed 2 Dissolving in 100mL deionized water to prepare zinc nitrate aqueous solution;
s2, feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in parallel flow at a flow rate of 5:1 by using a peristaltic pump, heating the mixed solution to 73 ℃ in a water bath while magnetically stirring at a speed of 300r/min, preserving heat, dripping 0.1mol/L sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 6
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 is weighed according to the molar ratio of zinc to aluminum of 344.6250g Zn(NO 3 ) 2 ·6H 2 O is dissolved in 600mL deionized water to prepare a sodium metaaluminate aqueous solution, and 4.1g NaAlO is weighed 2 Dissolving in 100mL deionized water to prepare zinc nitrate aqueous solution;
s2, feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in parallel flow at a flow rate of 6:1 by using a peristaltic pump, heating the mixed solution to 73 ℃ in a water bath while magnetically stirring at a speed of 300r/min, preserving heat, dripping 0.1mol/L sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 7
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 4.1g NaAlO 2 Respectively dissolving in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in parallel flow at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at the rotation speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, dripping 0.1mol/L dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 5, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 8
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 4.1g NaAlO 2 Respectively dissolving in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in parallel flow at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at the rotation speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, dripping 0.1mol/L dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 9, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 9
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 4.1g NaAlO 2 Respectively dissolving in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in parallel flow at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at the rotation speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, dripping 0.1mol/L dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Example 10
The embodiment provides a high-purity zinc aluminate spinel, and the preparation method comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 4.1g NaAlO 2 Respectively dissolving in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in parallel flow at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at the rotation speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, dripping 0.1mol/L dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after the titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminum spinel precursor prepared in the step S3 in a muffle furnace, heating to 650 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the high-purity zinc aluminum spinel.
Comparative example 1
The comparative example provides a zinc aluminate spinel, the preparation method of which comprises the following steps:
s1 weighing 15g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 100mL deionized water to prepare zinc nitrate aqueous solution, and 4.1g NaAlO is weighed 2 And 16.9Na 2 CO 3 Dissolving in 200ml deionized water to prepare a sodium metaaluminate precipitant solution;
s2, respectively dripping the zinc nitrate aqueous solution and the sodium metaaluminate precipitant solution prepared in the step S1 in parallel by using a separating funnel, magnetically stirring the mixed solution at the rotating speed of 300r/min, heating the mixed solution to 73 ℃ in a water bath, preserving heat, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminate spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the zinc aluminate spinel.
Comparative example 2
The comparative example provides a zinc aluminate spinel, the preparation method of which comprises the following steps:
s1 according to the zinc-aluminum mole ratio of 0.5, 7.4375g Zn (NO) 3 ) 2 ·6H 2 O and 18.7565g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 200mL deionized water to prepare a zinc nitrate aluminum nitrate solution, and 16.9g of Na is weighed 2 CO 3 Dissolving in 200ml deionized water to prepare a precipitant solution;
s2, feeding the zinc nitrate aluminum nitrate solution and the precipitator solution prepared in the step S1 in parallel flow by using a separating funnel, heating the mixed solution to 73 ℃ in a water bath under magnetic stirring at a rotating speed of 300r/min, preserving heat, controlling the pH value of the mixed solution to be 7, and standing and aging the mixed solution for 30min after titration is finished;
s3, carrying out suction filtration and washing on the mixed solution subjected to static aging in the step S2, and drying a filter cake obtained by washing in a drying oven at 100 ℃ for 12 hours to obtain a zinc aluminum spinel precursor;
and S4, placing the zinc aluminate spinel precursor prepared in the step S3 in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 5 hours to obtain the zinc aluminate spinel.
The gazelle spinels prepared in examples 1 to 10 and comparative examples 1 and 2 were subjected to phase analysis using X-ray powder diffraction, average crystal grain diameters of the gazelle spinels of the respective examples and comparative examples were calculated by the scherrer formula, and physical properties of the gazelle spinels of the respective examples and comparative examples were tested, and specific phases and physical index results are shown in table 1.
Table 1:
as can be seen from Table 1, the smaller the zinc-aluminum molar ratio, the smaller the prepared zinc-aluminum spinel crystal grain diameter, the larger the specific surface area, pore volume and pore diameter, and the pH range and roasting temperature of the solution during preparation also affect the zinc-aluminum spinel crystal grain diameter, which is reflected in that the larger the pH is, the higher the roasting temperature is, the larger the zinc-aluminum spinel crystal grain diameter is, and the smaller the specific surface area, pore volume and pore diameter are. Comparative example 1 is a zinc-aluminum spinel prepared by a traditional coprecipitation method, and the molar ratio of zinc to aluminum is relatively large, so that the prepared zinc-aluminum spinel contains a large amount of zinc oxide impurities and carbonate impurities, and the purity, specific surface area, pore volume and pore diameter are relatively small; comparative example 2 uses aluminum nitrate as an aluminum source, although the molar ratio of zinc to aluminum is 0.5, since aluminum ions and zinc ions are both metal cations, and cannot be directly reacted to form a precursor of a zinc-aluminum spinel structure, the formed zinc-aluminum spinel structure is formed by only mechanically mixing zinc-aluminum precipitates and then calcining, so that most of aluminum exists alone in the form of aluminum oxide in a catalyst, and thus the prepared zinc-aluminum spinel contains a large amount of aluminum oxide and carbonate impurities, and when the zinc-aluminum spinel is used as a catalyst to prepare other products, the acid sites of the aluminum oxide impurities tend to cause side reactions to occur, resulting in poor catalytic efficiency; in addition, both comparative examples 1 and 2 use carbonate as a precipitant, so that zinc aluminate spinel prepared by the method is easy to influence the preparation of products and aggravates carbon emission and pollutes the environment when the zinc aluminate spinel is used as a catalyst in the following process.
The high purity zinc aluminum tips of examples 1 to 3The spinel and the zinc aluminate spinel of comparative examples 1 and 2 were used in ethanol reforming hydrogen production reactions to evaluate the catalytic effect, the reaction being C 2 H 5 OH+3H 2 O＝2CO 2 +6H 2 Reaction conditions: the reaction time was 10h and the reaction temperature was 450 ℃. The evaluation results are shown in Table 2:
table 2:
as can be seen from table 2, when the zinc aluminate spinels of examples 1 to 3 were used for the catalytic reaction, the ethanol conversion rate and the hydrogen selectivity were higher, which were about 10% higher than those of comparative examples 1 and 2, because the catalysts of examples 1 to 3 were higher in purity, specific surface area, pore volume, pore diameter and smaller in grain size, and thus were higher in catalytic efficiency, and side reactions were effectively suppressed.
It should be understood that the foregoing examples of the present invention are merely illustrative of the present invention and are not intended to limit the present invention to the specific embodiments thereof. Any modification, equivalent replacement, improvement, etc. that comes within the spirit and principle of the claims of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The preparation method of the high-purity zinc aluminate spinel is characterized by comprising the following steps:
s1, respectively preparing a sodium metaaluminate aqueous solution and a zinc salt aqueous solution according to a proportion;
s2, slowly and parallelly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1, controlling the pH value of the mixed solution to be 5-10, and standing and aging the mixed solution after the titration is finished;
s3, filtering, washing and drying the mixed solution subjected to static aging in the step S2 to obtain a zinc aluminum spinel precursor;
s4, heating the zinc aluminate spinel precursor prepared in the step S3 to 400-900 ℃ at a heating rate of 1-3 ℃/min, and roasting for 4.5-10 hours to obtain the high-purity zinc aluminate spinel;
in the step S2, the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-3, and the mixed solution is heated to 50-90 ℃ for heat preservation in the slow parallel flow titration process of the sodium metaaluminate aqueous solution and the zinc salt aqueous solution; when the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-0.7, using an acid solution to supplement titration on the mixed solution; and when the molar ratio of the zinc salt to the sodium metaaluminate is 0.7-3, using an alkaline solution to supplement titration on the mixed solution, wherein the alkaline solution is sodium hydroxide.
2. The method for preparing high purity zinc aluminate spinel according to claim 1, wherein in step S2, the molar ratio of zinc salt to sodium metaaluminate is 0.5 to 1.5.
3. The method for preparing high-purity zinc aluminate spinel according to claim 1, wherein in step S2, the mixed solution is stirred at a rotation speed of 100-500 r/min during slow parallel flow titration of the sodium metaaluminate aqueous solution and the zinc salt aqueous solution; and the static aging time of the mixed solution is 20-60 min.
4. The method for preparing high purity zinc aluminate spinel according to claim 1, wherein the acidic solution is a mixture of one or more of dilute nitric acid, dilute hydrochloric acid, and dilute sulfuric acid.
5. The method for preparing high purity zinc aluminate spinel according to claim 1, wherein the zinc salt is one or more of zinc chloride, zinc nitrate or zinc sulfate.
6. The method for preparing high-purity zinc aluminate spinel according to claim 1, wherein in the step S3, the washed filter cake is dried at 60-100 ℃ for 8-12 hours.
7. A high-purity zinc aluminate spinel, characterized in that it has a specific surface area of 140 to 240m, and is produced by the process for producing a high-purity zinc aluminate spinel according to any one of claims 1 to 6 2 ·g -1 The grain diameter is 3-30 nm, the aperture is 2-30 nm, and the pore volume is 0.15-0.90 cm 3 /g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223631.4A CN114735730B (en) | 2022-03-09 | 2022-03-09 | High-purity zinc aluminate spinel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223631.4A CN114735730B (en) | 2022-03-09 | 2022-03-09 | High-purity zinc aluminate spinel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114735730A CN114735730A (en) | 2022-07-12 |
| CN114735730B true CN114735730B (en) | 2023-11-07 |
Family
ID=82274685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210223631.4A Active CN114735730B (en) | 2022-03-09 | 2022-03-09 | High-purity zinc aluminate spinel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114735730B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400431A (en) * | 1980-09-04 | 1983-08-23 | The Dow Chemical Company | Magnesium aluminum spinels |
| US5108979A (en) * | 1991-02-25 | 1992-04-28 | Intercat, Inc. | Synthetic spinels and processes for making them |
| CN102583467A (en) * | 2012-02-24 | 2012-07-18 | 山东大学 | Method using hydrotalcite-like substance with low zinc-aluminum molar ratio as precursor to manufacture zinc-aluminum spinel |
| CN106622204A (en) * | 2015-10-30 | 2017-05-10 | 中国石油天然气股份有限公司 | A zinc oxide material containing zinc-aluminate spinel and a preparing method thereof |
-
2022
- 2022-03-09 CN CN202210223631.4A patent/CN114735730B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400431A (en) * | 1980-09-04 | 1983-08-23 | The Dow Chemical Company | Magnesium aluminum spinels |
| US5108979A (en) * | 1991-02-25 | 1992-04-28 | Intercat, Inc. | Synthetic spinels and processes for making them |
| CN102583467A (en) * | 2012-02-24 | 2012-07-18 | 山东大学 | Method using hydrotalcite-like substance with low zinc-aluminum molar ratio as precursor to manufacture zinc-aluminum spinel |
| CN106622204A (en) * | 2015-10-30 | 2017-05-10 | 中国石油天然气股份有限公司 | A zinc oxide material containing zinc-aluminate spinel and a preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王 鹏.降低催化裂化汽油硫含量助剂的研究.《石油学报》.2003,第19卷(第2期),第70-76页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114735730A (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1177765C (en) | Cerium oxide and zirconium oxide based compsn., method of prepn.and utilisation in catalysis | |
| US20060088463A1 (en) | Process for preparing zirconium-cerium-based mixed oxides | |
| EP0841304B1 (en) | Zirconia fine powder and method for its production | |
| CN101696034B (en) | Method for preparing nano-cerium oxide and zirconia solid solution | |
| CN103908959B (en) | Ce-Zr composite alumina oxide material and preparation method thereof | |
| CN101007285B (en) | Organic-inorganic hybrid hydrotalcite-like heteropoly acid-supported catalyst | |
| CN112371105B (en) | Niobium pentoxide/titanium dioxide composite photocatalyst and preparation method and application thereof | |
| Krivtsov et al. | Exceptional thermal stability of undoped anatase TiO 2 photocatalysts prepared by a solvent-exchange method | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| RU2005137188A (en) | METHOD FOR PREPARING ZIRCONIUM OXIDES AND MIXED OXIDES ON ZIRCONIUM BASIS | |
| CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
| JP4972868B2 (en) | Surface-modified ceria / zirconia hydrated oxide, oxide thereof, production method thereof, and use thereof | |
| CN114735730B (en) | High-purity zinc aluminate spinel and preparation method thereof | |
| CN113860341A (en) | High-purity flaky boehmite and preparation method thereof | |
| CN111482179B (en) | Low-temperature Cu-series conversion catalyst and preparation method and application thereof | |
| CN110937620A (en) | Non-stoichiometric zinc-aluminum spinel and preparation method thereof | |
| CN113134352A (en) | Composite metal oxide catalyst for catalyzing direct decomposition of nitrogen oxide and preparation method thereof | |
| RU2506228C1 (en) | Method of obtaining mesoporous nanosized cerium dioxide powder (versions) | |
| CN115591541A (en) | CeO doped with high-valence niobium metal ions 2 Preparation method and application thereof | |
| CN111569891B (en) | Medium-temperature methane partial oxidation catalyst and preparation method and application thereof | |
| JP2005247585A (en) | Method for producing zirconia-ceria compound oxide powder | |
| JPH0535017B2 (en) | ||
| KR102255059B1 (en) | Method for preparing high efficiency ceria catalyst for air pollution purification using hydrothermal synthesis | |
| CN114620757B (en) | Green synthesis method of perovskite lanthanum cuprate nanosheet | |
| CN114887612B (en) | Composite oxide carrier and preparation method thereof, catalyst and preparation method and application thereof |
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 |