CN103191748A - Preparation method of sisal hemp-shaped CuO-ZnO composite oxide - Google Patents
Preparation method of sisal hemp-shaped CuO-ZnO composite oxide Download PDFInfo
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- CN103191748A CN103191748A CN2013101253169A CN201310125316A CN103191748A CN 103191748 A CN103191748 A CN 103191748A CN 2013101253169 A CN2013101253169 A CN 2013101253169A CN 201310125316 A CN201310125316 A CN 201310125316A CN 103191748 A CN103191748 A CN 103191748A
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Abstract
The invention discloses a preparation method of sisal hemp-shaped CuO-ZnO composite oxide, and belongs to the technical field of inorganic functional material preparation technology and high-energy solid propellants. The preparation method comprises the following steps of: adding an amine chelating agent into a mixed solution of soluble copper salt and zinc salt at first to form a chelate solution; fully chelating metal ions and the chelating agent by stirring; adding an alkali metal hydroxide solution into a reaction system; controlling reaction temperature to obtain a composite oxide precipitate; and filtering, washing and drying to obtain CuO-ZnO composite oxide having a sisal hemp structure. The preparation method has the advantages that the CuO-ZnO composite oxide for ammonium persulfate (AP) catalysis is prepared; the CuO-ZnO composite oxide prepared by using the provided method has a novel structure and is sisal hemp-shaped; the high-temperature decomposition temperature is reduced to 120 DEG C, and the oxide is high in performance; and the method provided by the invention is simple in reaction process, mild in conditions, short in procedures and suitable for industrial production.
Description
Technical field
The invention belongs to inorganic functional material technology of preparing and high-energy solid propellant technical field, particularly a kind of preparation method of sisal hemp shape CuO-ZnO composite oxides.
Background technology
Solid propellant is the power source material of solid propellant rocket, plays an important role in guided missile and space technology development.Ammonium perchlorate (AP) is as the high energy component of composite solidpropellant, and content accounts for 60% ~ 80% ratio, and its thermal decomposition characteristic and propellant combustion characteristic are closely related.For improving the combustibility of solid propellant, need to add the combustion speed that catalyst such as transition metal oxide, metal simple-substance, metal complex and salt improve AP usually.Wherein transition metal oxide has advantages such as catalytic activity height, good stability, so practicality is best.
Cupric oxide is because inexpensive, nontoxic and chemical stability is strong, and AP is had significant catalytic action, is a kind of important burningrate catalyst.Because structure and the pattern of material have a significant impact its performance, many scholars have carried out preparation method and the Catalytic Performance of different-shape cupric oxide, have prepared the cupric oxide of different-shapes such as flower-shaped, needle-like, bar-shaped and shuttle shape.The Zinc oxide catalytic of a kind of taper of bibliographical information also has good catalytic effect to AP recently.
With respect to single metal oxide, the easier catalytic performance that shows excellence of composite metal oxide.Realize the variation of catalyst pattern and the lifting of performance thereof by the preparation compound catalyze material, become one of developing direction of catalytic field.The present invention has prepared sisal hemp shape CuO-ZnO composite oxide catalysts by the combination of cupric oxide and Zinc oxide catalytic advantage, has improved catalytic activity, greatly reduces the elevated temperature heat decomposition reaction temperature of AP.
Summary of the invention
The AP catalysis material that the objective of the invention is to prepare Stability Analysis of Structures, cheap, excellent performance and have a extensive future, and provide that a kind of technology is simple, the preparation method of sisal hemp shape CuO-ZnO composite oxide catalysts that mild condition, flow process are short.
Technical scheme of the present invention is: at first add the amine chelating agent in the aqueous solution of soluble copper salt and zinc salt and make chelate solution, make metal ion and the abundant chelating of chelating agent by stirring, in reaction system, add alkali hydroxide soln then, obtain oxide precipitation by the control reaction temperature.Through filtering, to wash, drying makes the CuO-ZnO composite oxides.By the ratio of copper ion and zinc ion in the adjusting initial soln, can make the CuO-ZnO composite oxides of different Cu zinc ratio.
Concrete preparation process is:
Compound concentration is the soluble copper salt of 0.5 ~ 1mol/L and the mixed solution of zinc salt under the normal temperature, magnetic agitation 5 ~ 30 min, under stirring condition, add the amine chelating agent, continue to stir 5 ~ 30 min, add alkali hydroxide soln again, the pH value that makes reaction system is 12 ~ 14, stirring 1 ~ 2h, is 40 ~ 100 ℃ in temperature, insulation 1-3h, filtration washing, the CuO-ZnO composite oxides that behind dry 12h under 60 ℃, obtain then; Wherein, the mol ratio of copper ion and zinc ion is 1 ~ 3:1 ~ 3, and chelating agent is 0.2 ~ 5:1 with the mol ratio of total metal ion (summation of copper ion and zinc ion), and alkali hydroxide soln concentration is 0.5 ~ 7 mol/L.
Described soluble copper salt, zinc salt comprise: the nitrate of copper, zinc, chloride, sulfate, phosphate, in one or more, preferably nitrate wherein.
Described amine comprises: ethylenediamine, 1,3-propane diamine, 1, a kind of in the 4-butanediamine, wherein preferred ethylenediamine.
Described alkali metal hydroxide comprises: NaOH, a kind of in the potassium hydroxide, wherein preferred NaOH.
The invention has the advantages that: (1) has prepared a kind of CuO-ZnO composite oxides of the AP of can be used for catalysis; (2) the CuO-ZnO composite oxides that prepare with method provided by the invention, novel structure (sisal hemp shape) and excellent performance (the high-temperature decomposition temperature reduction exceedes 120 ℃); (3), mild condition simple with method reaction process provided by the invention, flow process are short, are fit to suitability for industrialized production.
Description of drawings
The stereoscan photograph of the CuO-ZnO composite oxides that Fig. 1 obtains for the invention process case 1.
The X-ray diffractogram of the CuO-ZnO composite oxides that Fig. 2 obtains for the invention process case 1.
The CuO-ZnO composite oxides that Fig. 3 obtains for the invention process case 1 are to the DTG figure of AP catalysis.
The specific embodiment
Below in conjunction with concrete embodiment technical scheme of the present invention is described further.
Case study on implementation 1
Preparation 8ml concentration is the mixed solution of 0.75mol/L copper nitrate and zinc nitrate under the normal temperature, wherein the mol ratio of copper ion and zinc ion is 2:1, the ethylenediamine that under stirring condition, adds 0.0089mol, continue to stir 10 min, add the sodium hydroxide solution that 30ml concentration is 0.8 mol/L again, stir 10 min, then temperature control is kept 1h at 60 ℃, filtration washing, obtain end product CuO-ZnO composite oxides behind the dry 12h down at 60 ℃ then, the DTG that the scanned photograph of product, X-ray diffractogram reach AP catalysis schemes as Figure 1-3.As shown in Figure 1, the gained oxide is three-dimensional sisal hemp shape structure, and basic structural unit is nanometer rods, and the length of nanometer rods is at 2 ~ 4 μ m, and diameter is at 300 ~ 600nm.X-ray diffractogram shows that product is the composite oxides of copper zinc.DTG schemes demonstration, and pure AP is heated and shows as two sections decomposition, and first section is decomposed maximum decomposition temperature at 441 ℃, and first section is decomposed maximum decomposition temperature at 312 ℃; After adding gained CuO-ZnO composite oxides, have only a decomposition peak (278 ℃) on the DTG curve of mixture, the decomposition peak has shifted to an earlier date 163 ℃.
Case study on implementation 2
Preparation 8ml concentration is the mixed solution of 0.75mol/L copper nitrate and zinc nitrate under the normal temperature, wherein the mol ratio of copper ion and zinc ion is 1:1, the ethylenediamine that under stirring condition, adds 0.0089mol, continue to stir 10 min, add the sodium hydroxide solution that 48ml concentration is 0.8 mol/L again, stir 10 min, then temperature control is kept 1h at 60 ℃, filtration washing obtains end product CuO-ZnO composite oxides behind the dry 12h down at 60 ℃ then.
Case study on implementation 3
Preparation 8ml concentration is the mixed solution of 0.75mol/L copper nitrate and zinc nitrate under the normal temperature, wherein the mol ratio of copper ion and zinc ion is 1:2, the ethylenediamine that under stirring condition, adds 0.0089mol, continue to stir 10 min, add the sodium hydroxide solution that 30ml concentration is 0.8 mol/L again, stir 10 min, then temperature control is kept 1h at 60 ℃, filtration washing obtains end product CuO-ZnO composite oxides behind the dry 12h down at 60 ℃ then.
Case study on implementation 4
Preparation 8ml concentration is the mixed solution of 0.75mol/L copper nitrate and zinc nitrate under the normal temperature, wherein the mol ratio of copper ion and zinc ion is 1:3, the ethylenediamine that under stirring condition, adds 0.0089mol, continue to stir 10 min, add the sodium hydroxide solution that 30ml concentration is 0.8 mol/L again, stir 10 min, then temperature control is kept 1h at 60 ℃, filtration washing obtains end product CuO-ZnO composite oxides behind the dry 12h down at 60 ℃ then.
Case study on implementation 5
Preparation 8ml concentration is the mixed solution of 0.75mol/L copper nitrate and zinc nitrate under the normal temperature, wherein the mol ratio of copper ion and zinc ion is 3:1, the ethylenediamine that under stirring condition, adds 0.0089mol, continue to stir 10 min, add the sodium hydroxide solution that 30ml concentration is 0.8 mol/L again, stir 10 min, then temperature control is kept 1h at 60 ℃, filtration washing obtains end product CuO-ZnO composite oxides behind the dry 12h down at 60 ℃ then.
Claims (7)
1. the preparation method of sisal hemp shape CuO-ZnO composite oxides is characterized in that: comprise the steps:
Compound concentration is the soluble copper salt of 0.5 ~ 1mol/L and the mixed solution of zinc salt under the normal temperature, magnetic agitation 5 ~ 30 min, under stirring condition, add the amine chelating agent, continue to stir 5 ~ 30 min, add alkali hydroxide soln again, the pH value that makes reaction system is 12 ~ 14, stirring 1 ~ 2h, is 40 ~ 100 ℃ in temperature, insulation 1-3h, filtration washing, the CuO-ZnO composite oxides that behind dry 12h under 60 ℃, obtain then; Wherein, the mol ratio of copper ion and zinc ion is 1 ~ 3:1 ~ 3 in the mixed solution of soluble copper salt and zinc salt, and the amine chelating agent is 0.2 ~ 5:1 with the mol ratio of total metal ion, and alkali hydroxide soln concentration is 0.5 ~ 7 mol/L.
2. the preparation method of sisal hemp shape CuO-ZnO composite oxides according to claim 1, it is characterized in that: described soluble copper salt, zinc salt comprise: the nitrate of copper, zinc, chloride, sulfate, phosphate, in one or more.
3. the preparation method of sisal hemp shape CuO-ZnO composite oxides according to claim 1 and 2, it is characterized in that: described soluble copper salt, zinc salt are nitrate.
4. the preparation method of sisal hemp shape CuO-ZnO composite oxides according to claim 1, it is characterized in that: described amine chelating agent comprises: ethylenediamine, 1,3-propane diamine, 1, a kind of in the 4-butanediamine.
5. according to the preparation method of claim 1 or 4 described sisal hemp shape CuO-ZnO composite oxides, it is characterized in that: described amine chelating agent is ethylenediamine.
6. the preparation method of sisal hemp shape CuO-ZnO composite oxides according to claim 1, it is characterized in that: described alkali metal hydroxide comprises: NaOH, a kind of in the potassium hydroxide.
7. according to the preparation method of claim 1 or 6 described sisal hemp shape CuO-ZnO composite oxides, it is characterized in that: described alkali metal hydroxide is NaOH.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827367A (en) * | 2017-11-23 | 2018-03-23 | 海南中航特玻科技有限公司 | A kind of preparation method with anti-dazzle anti-reflection function plate glass |
| CN113457707A (en) * | 2021-06-29 | 2021-10-01 | 湖北航泰科技有限公司 | Core-shell-structure ZnCo @ NPC nanomaterial based on MOFs and preparation method thereof |
| CN114177910A (en) * | 2021-11-08 | 2022-03-15 | 深圳净昕环境健康技术有限公司 | Copper oxide and zinc oxide composite piezoelectric photocatalytic material and preparation method and application thereof |
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| WO2008116104A1 (en) * | 2007-03-21 | 2008-09-25 | Battelle Energy Alliance, Llc | A precursor of a catalytic structure, a catalytic structure, a method of fabricating the same, and a system and a method for using the same |
| CN101549289A (en) * | 2009-05-12 | 2009-10-07 | 武汉大学 | Nucleocapsid energizing agent for propelling agent and method for preparing same |
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- 2013-04-11 CN CN201310125316.9A patent/CN103191748B/en not_active Expired - Fee Related
Patent Citations (3)
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| EP0705808A1 (en) * | 1994-10-05 | 1996-04-10 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Propellant based on phase-stabilized ammonium nitrate |
| WO2008116104A1 (en) * | 2007-03-21 | 2008-09-25 | Battelle Energy Alliance, Llc | A precursor of a catalytic structure, a catalytic structure, a method of fabricating the same, and a system and a method for using the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827367A (en) * | 2017-11-23 | 2018-03-23 | 海南中航特玻科技有限公司 | A kind of preparation method with anti-dazzle anti-reflection function plate glass |
| CN113457707A (en) * | 2021-06-29 | 2021-10-01 | 湖北航泰科技有限公司 | Core-shell-structure ZnCo @ NPC nanomaterial based on MOFs and preparation method thereof |
| CN113457707B (en) * | 2021-06-29 | 2023-11-21 | 湖北航泰科技有限公司 | MOFs-based core-shell structure ZnCo@NPC nanomaterial and preparation method thereof |
| CN114177910A (en) * | 2021-11-08 | 2022-03-15 | 深圳净昕环境健康技术有限公司 | Copper oxide and zinc oxide composite piezoelectric photocatalytic material and preparation method and application thereof |
| CN114177910B (en) * | 2021-11-08 | 2024-02-23 | 深圳净昕环境健康技术有限公司 | Copper oxide and zinc oxide composite piezoelectric electro-optic catalytic material and preparation method and application thereof |
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