CN114735730A - High-purity zinc-aluminum spinel and preparation method thereof - Google Patents
High-purity zinc-aluminum spinel and preparation method thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 118
- 239000011029 spinel Substances 0.000 title claims abstract description 118
- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims abstract description 65
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 96
- 239000011259 mixed solution Substances 0.000 claims abstract description 92
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 83
- -1 zinc aluminate Chemical class 0.000 claims abstract description 66
- 239000007864 aqueous solution Substances 0.000 claims abstract description 56
- 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 49
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 49
- 239000011734 sodium Substances 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 150000003751 zinc Chemical class 0.000 claims abstract description 33
- 238000004448 titration Methods 0.000 claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 18
- 230000003068 static effect Effects 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000012266 salt solution Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 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
- 239000012716 precipitator Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229910052782 aluminium Inorganic materials 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000005303 weighing Methods 0.000 description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 description 11
- 230000002572 peristaltic effect Effects 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052566 spinel group Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012071 phase 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
- 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
- 230000002378 acidificating effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-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
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003795 chemical substances by application Substances 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
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons 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
- 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
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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-
- 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
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- 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
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P2006/14—Pore volume
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- 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
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- 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
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Abstract
The invention relates to the field of preparation of zinc aluminate spinel, in particular to high-purity zinc aluminate spinel and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing sodium metaaluminate aqueous solution and zinc salt aqueous solution according to the proportion; s2, slowly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a parallel flow manner, controlling the pH value of the mixed solution, and standing and aging the mixed solution after titration; s3, carrying out suction filtration, washing and drying on the static aged mixed solution obtained in the step S2 to obtain a zinc-aluminum spinel precursor; s4, heating the zinc aluminate spinel precursor prepared in the step S4 to high temperature and roasting at the high temperature to obtain the high-purity zinc aluminate spinel; in step S2, the molar ratio of the sodium metaaluminate to the zinc salt is 0.5-3. The preparation method reduces the zinc-aluminum ratio, does not introduce additional precipitator, and improves the purity, the dispersity and the specific surface area of the prepared zinc-aluminum spinel.
Description
Technical Field
The invention relates to the field of preparation of zinc aluminate spinel, and particularly relates to high-purity zinc aluminate spinel and a preparation method thereof.
Background
Zinc aluminium spinel (ZnAl)2O4) Is AB2O4The spinel type ternary oxide semiconductor with zinc ions in tetrahedral plane (A site) and aluminum ions in octahedral plane (B site) typical in the chemical formula has been considered as a functional material with a variety of potential application prospects, and benefits from ZnAl2O4Has the characteristics of high thermal stability, good acid and alkali resistance, high mechanical strength, low acidity, large specific surface area and wide band gap energy (-3.8 eV), can be used as a photoelectronic device activated in an ultraviolet region, 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 catalytic carrier of zinc aluminate spinel with very high surface energy and grain boundary energy, can inhibit the growth of crystal grains, 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 function of catalytic efficiency, and is widely used for the reaction of preparing methanol from carbon dioxide, the high-temperature water-vapor transformation reaction (HT-WGS), the carbonylation reaction, the oxidation reaction of propane, the hydrogen production reaction of hydrogen, the Fischer-Tropsch synthesis, the catalytic combustion of hydrocarbon, the preparation of olefin from low-carbon alkane through dehydrogenation, The organic pollutants are degraded by photocatalysis and the desulfurization of gasoline and diesel oil is carried out.
The preparation method of the zinc-aluminum 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 product purity, poor uniformity and small specific surface area; the sol-gel method requires the use of expensive metalsThe popularization and the use are limited due to the overhigh cost of alkoxide, and the prepared zinc-aluminum spinel has poor sintering resistance; the hydrothermal synthesis method has strict requirements on reaction equipment, high operation requirements and difficult popularization to large-scale production, and the prepared zinc-aluminum spinel has large crystal grains and poor dispersibility. Compared with the method, the coprecipitation method has the advantages of 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 drop a mixed salt solution mixed with zinc salt and aluminum salt into deionized water simultaneously or sequentially with sodium carbonate or sodium hydroxide to precipitate zinc-aluminum hydrotalcite layered double hydroxide (Zn-Al-LDH), and then to obtain zinc-aluminum spinel by high-temperature roasting. This process requires a high zinc to aluminium ratio, typically 1 in molar ratio<Zn2+/Al3+<4, since the molar ratio of zinc to aluminum is much higher than the stoichiometric ratio, oxide impurities such as zinc oxide and aluminum oxide can be generated, the purity of the zinc aluminate spinel is low, further acid-base treatment is needed to obtain pure-phase zinc aluminate spinel, and when the zinc aluminate spinel is used as a catalyst for preparing other products, the acid sites of the aluminum oxide impurities can cause side reactions.
At present, there are also some prior arts which improve the conventional coprecipitation method to reduce the molar ratio of zinc and aluminum, however, these methods still need to introduce carbonate (such as sodium carbonate), urea, etc. as precipitant, the generated zinc aluminate spinel precursor is double hydroxide (LDH-CO3) containing carbonate between sheets, the carbonate impurity is harmful in the preparation process of some chemical products (such as polymer additive), and needs to be controlled and reduced as much as possible, and the carbonate impurity will emit carbon dioxide in the roasting process to increase carbon emission.
Disclosure of Invention
The present invention is directed to overcoming at least one of the disadvantages of the prior art, and to providing a high purity zinc aluminum spinel and a method for preparing the same, which reduces the zinc aluminum ratio, does not introduce additional precipitant, and improves the purity, dispersibility, and specific surface area of the prepared zinc aluminum spinel.
The technical scheme adopted by the invention is to provide a preparation method of high-purity zinc-aluminum spinel, which comprises the following steps:
s1, respectively preparing a sodium metaaluminate aqueous solution and a zinc salt aqueous solution according to the proportion;
s2, slowly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a parallel flow manner, controlling the pH value of the mixed solution, and standing and aging the mixed solution after titration;
s3, carrying out suction filtration, washing and drying on the static aged mixed solution obtained in the step S2 to obtain a zinc-aluminum spinel precursor;
s4, heating the zinc aluminate spinel precursor prepared in the step S3 to high temperature and roasting at the high temperature to obtain the high-purity zinc aluminate spinel;
in step S2, the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-3.
In the technical scheme, the molar ratio of a zinc source to an aluminum source is reduced to 0.5-3 from 1-4 of a common preparation method, so that oxide impurities such as zinc oxide and the like in a roasted product are greatly reduced, sodium metaaluminate is used as the 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 structure is generated by coprecipitation after neutralization and aging reaction with zinc salt, and is nitrate radical double hydroxide (Zn-Al-LDH-NO) with low molar ratio of zinc and aluminum3) After coprecipitation roasting, metaaluminate can be completely combined with zinc ions to form a zinc-aluminum spinel structure, and because no additional precipitating agent such as common carbonate, urea and the like is added in the coprecipitation process, carbonate-free double hydroxide (LDH-CO) is not contained between zinc-aluminum spinel sheets3) Impurities; by controlling the molar ratio of zinc to aluminum and omitting an extra added precipitator, the purity of the zinc-aluminum spinel is controlled from the molecular level, oxide impurities and carbon emission generated by roasting are avoided, the atom utilization rate and the preparation efficiency are improved to the maximum extent, a roasted product does not need to be further treated, the size of a prepared zinc-aluminum spinel crystal grain 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 green and environment-friendly.
Further, in step S2, the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-1.5.
Further, in step S2, heating the mixed solution to 50-90 ℃ while stirring at a rotation speed of 100-500 r/min, and preserving heat, during the slow parallel flow titration of the sodium metaaluminate aqueous solution and the zinc salt aqueous solution; controlling the pH value of the mixed solution to be 5-10; and the static aging time of the mixed solution is 20-60 min.
Further, when the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-0.7, carrying out additional titration on the mixed solution by using an acidic solution; and when the molar ratio of the zinc salt to the sodium metaaluminate is 0.7-3, carrying out supplementary titration on the mixed solution by using an alkaline solution.
Still further, the acid solution is one or a mixture of more of dilute nitric acid, dilute hydrochloric acid and dilute sulfuric acid, and/or the alkaline solution is one or a mixture of more of sodium hydroxide, sodium carbonate, ammonium bicarbonate, urea and ammonia water.
And further, after the mixed solution is subjected to supplementary titration by using one or more of a mixture of sodium carbonate, ammonium bicarbonate, urea and ammonia water, the acid solution is dripped to remove impurities.
Preferably, after the mixed solution is subjected to supplementary titration by using a mixture of 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 using amount of sodium metaaluminate is large, the alkalinity of a solution system is strong, so that a small amount of acidic solution is needed to control the pH value of the system; when the using amount of the zinc salt is large, the solution system is biased to be acidic, a small amount of alkaline solution except sodium metaaluminate is added to adjust the pH value, the molar ratio of zinc and aluminum in the solution cannot be changed, and when alkaline solution containing carbonate or urea and the like is used, acidic solution is added subsequently to remove carbonate, so that carbonate impurities are not contained in the zinc aluminate spinel precursor.
Further, the zinc salt is one or a mixture of zinc chloride, zinc nitrate or zinc sulfate.
Further, in step S3, the washed filter cake is dried at 60-100 ℃ for 8-12 h.
Further, in 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 hours.
The invention also provides high-purity zinc aluminate spinel prepared by the preparation method, and the specific surface area of the high-purity zinc aluminate spinel is 140-240m2·g-1The grain diameter is 3-30 nm, the pore diameter is 2-30 nm, and the pore volume is 0.15-0.90 cm3/g。
In the technical scheme, sodium metaaluminate and zinc salt are used as raw materials, the high-purity zinc aluminate spinel with a mesoporous structure is prepared by a coprecipitation method, the specific surface area, the pore diameter and the pore volume 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 and 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 and the like in the prepared zinc-aluminum spinel is reduced, the preparation method prepares the zinc-aluminum spinel with a mesoporous structure by direct roasting, the preparation method is simple and efficient, a high-purity product can be obtained without further acid-base treatment, the specific surface area, the aperture 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 extra 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 the product is not influenced in the application process.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst according to example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a catalyst according to example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of a catalyst according to 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 only for purposes of illustration and are not to be construed as limiting the invention. For a better understanding of the following embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood 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 a preparation method thereof comprises the following steps:
s1 weighing 7.4375g Zn (NO) according to the molar ratio of zinc to aluminum of 0.53)2·6H2O and 4.1g NaAlO2Respectively dissolving the sodium metaaluminate solution and the zinc nitrate solution in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, respectively feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a cocurrent manner at the same flow rate by using a peristaltic pump, carrying out magnetic stirring on the mixed solution at the rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 2
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 14.8750g Zn (NO) according to the molar ratio of zinc to aluminum being 13)2·6H2Dissolving O in 200mL deionized water to obtain sodium metaaluminate aqueous solution, and weighing 4.1g NaAlO2Dissolving the zinc nitrate into 100mL of deionized water to prepare a zinc nitrate aqueous solution;
s2, respectively feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in a cocurrent manner at a flow rate of 2:1 by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 3
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 22.3125g Zn (NO) according to the molar ratio of zinc to aluminum of 1.53)2·6H2Dissolving O in 300mL deionized water to prepare sodium metaaluminate aqueous solution, weighing 4.1g NaAlO2Dissolving in 100mL of deionized water to prepare a zinc nitrate aqueous solution;
s2, respectively feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in a cocurrent manner at a flow rate of 3:1 by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 high-purity zinc aluminate spinel.
Example 4
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 29.7500g Zn (NO) according to the molar ratio of zinc to aluminum being 23)2·6H2Dissolving O in 400mL deionized water to obtain sodium metaaluminate aqueous solution, and weighing 4.1g NaAlO2Dissolving in 100mL of deionized water to prepare a zinc nitrate aqueous solution;
s2, respectively feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in a cocurrent manner at a flow rate of 4:1 by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 high-purity zinc aluminate spinel.
Example 5
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 37.1875g Zn (NO) according to the molar ratio of zinc to aluminum of 2.53)2·6H2Dissolving O in 500mL deionized water to obtain sodium metaaluminate aqueous solution, and weighing 4.1g NaAlO2Dissolving in 100mL of deionized water to prepare a zinc nitrate aqueous solution;
s2, respectively feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in a cocurrent manner at a flow rate of 5:1 by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 6
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 44.6250g Zn (NO) according to the molar ratio of zinc to aluminum being 33)2·6H2Dissolving O in 600mL deionized water to obtain sodium metaaluminate aqueous solution, and weighing 4.1g NaAlO2Dissolving in 100mL of deionized water to prepare a zinc nitrate aqueous solution;
s2, respectively feeding the zinc salt aqueous solution and the sodium metaaluminate aqueous solution prepared in the step S1 in a cocurrent manner at a flow rate of 6:1 by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of sodium hydroxide solution into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 7
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 molar ratio of Zn to Al7.4375g Zn (NO) were weighed in a ratio of 0.53)2·6H2O and 4.1g NaAlO2Respectively dissolving the sodium metaaluminate solution and the zinc nitrate solution in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, respectively feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a cocurrent manner at the same flow rate by using a peristaltic pump, carrying out magnetic stirring on the mixed solution at the rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 5, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 8
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 7.4375g Zn (NO) according to the molar ratio of zinc to aluminum of 0.53)2·6H2O and 4.1g NaAlO2Respectively dissolving the sodium metaaluminate solution and the zinc nitrate solution in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, respectively feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a cocurrent manner at the same flow rate by using a peristaltic pump, carrying out magnetic stirring on the mixed solution at the rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 9, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Example 9
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 7.4375g Zn (NO) according to the molar ratio of zinc to aluminum of 0.53)2·6H2O and 4.1g NaAlO2Respectively dissolving the sodium metaaluminate solution and the zinc nitrate solution in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, respectively feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a cocurrent manner at the same flow rate by using a peristaltic pump, magnetically stirring the mixed solution at a rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
s4, placing the zinc aluminate spinel precursor prepared in the step S3 in a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and roasting for 5h to obtain the high-purity zinc aluminate spinel.
Example 10
The embodiment provides a high-purity zinc aluminate spinel, and a preparation method thereof comprises the following steps:
s1 weighing 7.4375g Zn (NO) according to the molar ratio of zinc to aluminum of 0.53)2·6H2O and 4.1g NaAlO2Respectively dissolving the sodium metaaluminate solution and the zinc nitrate solution in 100mL of deionized water to prepare a sodium metaaluminate aqueous solution and a zinc nitrate aqueous solution;
s2, respectively feeding the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a cocurrent manner at the same flow rate by using a peristaltic pump, carrying out magnetic stirring on the mixed solution at the rotation speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, preserving the heat, dripping 0.1mol/L of dilute nitric acid into the mixed solution by using a separating funnel, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the high-purity zinc-aluminum spinel.
Comparative example 1
The comparative example provides a zinc aluminate spinel, the method of preparation including the steps of:
s1 weighing 15g Zn (NO)3)2·6H2Dissolving O in 100mL deionized water to obtain zinc nitrate aqueous solution, and weighing 4.1g NaAlO2And 16.9Na2CO3Dissolving in 200ml deionized water to prepare sodium metaaluminate precipitator solution;
s2, respectively dripping the zinc nitrate aqueous solution and the sodium metaaluminate precipitator solution prepared in the step S1 in a cocurrent manner by using a separating funnel, carrying out magnetic stirring on the mixed solution at the rotating speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, keeping the temperature, controlling the pH of the mixed solution to be 7, and after the titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the zinc aluminate spinel.
Comparative example 2
The comparative example provides a zinc aluminate spinel, the method of preparation including the steps of:
s1 weighing 7.4375g Zn (NO) according to the molar ratio of zinc to aluminum of 0.53)2·6H2O and 18.7565g Al (NO)3)3·9H2Dissolving O in 200mL of deionized water to prepare a zinc nitrate aluminum nitrate solution, and weighing 16.9g of Na2CO3Dissolving in 200ml deionized water to prepare a precipitant solution;
s2, respectively feeding the zinc nitrate aluminum nitrate solution prepared in the step S1 and the precipitator solution in a cocurrent manner by using a separating funnel, magnetically stirring the mixed solution at a rotating speed of 300r/min while heating the mixed solution in a water bath to 73 ℃, keeping the temperature, controlling the pH of the mixed solution to be 7, and after titration is finished, standing and aging the mixed solution for 30 min;
s3, carrying out suction filtration and washing on the static aged mixed solution obtained in the step S2, and placing a washed filter cake into an oven to be dried for 12 hours at the temperature of 100 ℃ to obtain a zinc-aluminum spinel precursor;
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 5h to obtain the zinc aluminate spinel.
Phase analysis was performed on the zinc aluminum spinels prepared in examples 1 to 10 and comparative examples 1 and 2 using X-ray powder diffraction, the average grain diameters of the zinc aluminum spinels of each example and comparative example were calculated by the scherrer equation, and physical property tests were performed on the zinc aluminum spinels of each example and comparative example, with specific phase and physical index results as shown in table 1.
Table 1:
as can be seen from table 1, the smaller the molar ratio of zinc to aluminum, the smaller the grain diameter of the prepared zinc aluminate spinel, the larger the specific surface area, pore volume and pore diameter, and the larger the pH range and calcination temperature of the solution during preparation also affect the grain diameter of the zinc aluminate spinel, which is reflected in that the larger the pH, the higher the calcination temperature, the larger the grain diameter of the zinc aluminate spinel, and the smaller the specific surface area, pore volume and pore diameter. Comparative example 1 is that zinc-aluminum spinel prepared by a traditional coprecipitation method has a large molar ratio of zinc and aluminum, 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 correspondingly small; comparative example 2 using 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 directly react to form a precursor of a zinc-aluminum spinel structure, and the formed zinc-aluminum spinel structure is formed only by mechanically mixing and then calcining zinc-aluminum precipitates, most of aluminum exists alone in the catalyst in the form of alumina, so that the prepared zinc-aluminum spinel contains a large amount of alumina and carbonate impurities, and when the zinc-aluminum spinel is used as a catalyst to prepare other products, the acidic sites of the alumina impurities may possibly cause side reactions, resulting in low catalytic efficiency; in addition, in comparative examples 1 and 2, carbonate is used as a precipitator, so that the prepared zinc aluminum spinel is easy to influence the preparation of products when being subsequently used as a catalyst, and the carbon emission is aggravated to pollute the environment.
The high-purity zinc aluminate spinels of examples 1 to 3 and the zinc aluminate spinels of comparative examples 1 and 2 were used in the reaction for producing hydrogen by ethanol reforming to evaluate the catalytic effect thereof, and the reaction was C2H5OH+3H2O＝2CO2+6H2And the reaction conditions are as follows: the reaction time is 10h, and the reaction temperature is 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 are used in catalytic reactions, the ethanol conversion rate and the hydrogen selectivity are higher, both by about 10% than those of comparative examples 1 and 2, because the catalysts of examples 1 to 3 have higher purity, specific surface area, pore volume and pore diameter, and smaller grain size, the catalytic efficiency is higher, and side reactions can be effectively inhibited from proceeding.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. A preparation method of 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 the proportion;
s2, slowly titrating the sodium metaaluminate aqueous solution and the zinc salt aqueous solution prepared in the step S1 in a parallel flow manner, controlling the pH value of the mixed solution, and after the titration is finished, statically aging the mixed solution;
s3, carrying out suction filtration, washing and drying on the static aged mixed solution obtained in the step S2 to obtain a zinc-aluminum spinel precursor;
s4, heating the zinc aluminate spinel precursor prepared in the step S3 to high temperature and roasting at the high temperature to obtain the high-purity zinc aluminate spinel;
in step S2, the molar ratio of the zinc salt to the sodium metaaluminate is 0.5-3.
2. The method for preparing high purity zinc aluminate spinel according to claim 1, wherein the molar ratio of the zinc salt to the sodium metaaluminate is 0.5 to 1.5 in step S2.
3. The method for preparing high purity zinc aluminate spinel according to claim 1, wherein in step S2, the mixed solution of sodium metaaluminate solution and zinc salt solution is heated to 50-90 ℃ while stirring at a rotation speed of 100-500 r/min and maintaining the temperature during slow cocurrent flow titration; controlling the pH value of the mixed solution to be 5-10; 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 or 3, wherein when the molar ratio of the zinc salt to the sodium metaaluminate is 0.5 to 0.7, the mixed solution is subjected to additional titration by using an acidic solution; and when the molar ratio of the zinc salt to the sodium metaaluminate is 0.7-3, carrying out supplementary titration on the mixed solution by using an alkaline solution.
5. The method for preparing high purity zinc aluminate spinel according to claim 4, wherein the acidic solution is one or more of diluted nitric acid, diluted hydrochloric acid, and diluted sulfuric acid, and/or the alkaline solution is one or more of sodium hydroxide, sodium carbonate, ammonium bicarbonate, urea, and ammonia water.
6. The method for preparing high purity zinc aluminate spinel according to claim 5, wherein the acid solution is added dropwise to remove impurities after the mixed solution is subjected to supplementary titration with a mixture of one or more of sodium carbonate, ammonium bicarbonate, urea and ammonia water.
7. 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.
8. The preparation method of high-purity zinc aluminate spinel according to claim 1, wherein in step S3, the washed filter cake is dried at 60-100 ℃ for 8-12 h.
9. The preparation method of high-purity zinc aluminate spinel according to claim 1, wherein in 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.
10. A high purity zinc aluminate spinel prepared by the method of any one of claims 1 to 9, wherein the high purity zinc aluminate spinel has a specific surface area of 140-240m2·g-1The grain diameter is 3 to 30nm, a pore diameter of 2-30 nm, and a pore volume of 0.15-0.90 cm3/g。
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| WO2024087839A1 (en) * | 2022-10-24 | 2024-05-02 | 国家能源投资集团有限责任公司 | Co2 reversible adsorption material, composition and regeneration method thereof, and co2 capture method |
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