CN101863725A - Method for preparing nano catalytic composite materials by utilizing integrating process of ultrasonic-film-anti-solvent method - Google Patents
Method for preparing nano catalytic composite materials by utilizing integrating process of ultrasonic-film-anti-solvent method Download PDFInfo
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- CN101863725A CN101863725A CN201010198073A CN201010198073A CN101863725A CN 101863725 A CN101863725 A CN 101863725A CN 201010198073 A CN201010198073 A CN 201010198073A CN 201010198073 A CN201010198073 A CN 201010198073A CN 101863725 A CN101863725 A CN 101863725A
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Abstract
The invention relates to a method for preparing nano catalytic composite materials by utilizing an integrating process of an ultrasonic-film-anti-solvent method, comprising the following steps of: (1) the ammonium porchlorate saturated solution preparation process: dissolving ammonium porchlorate into a proper solvent to prepare the ammonium porchlorate saturated solution at certain temperature; (2) the dispersing process of a nano catalyst: uniformly dispersing the nano catalyst into an anti-solvent under ultrasonic action; (3) the preparing process: adding the AP (ammonium porchlorate) saturated solution to a nonsolvent through a film tube under certain pressure, wherein after the anti-solvent carries out desolvation on the solvent, the ammonium porchlorate is separated out and covers on the surfaces of uniformly-dispersed nano particles to form the nano catalytic composite materials; (4) filtering and drying processes: firstly carrying out solid-liquid separation on nano composite particles; and (5) the drying process: drying separated materials at 50-150 DEG C to obtain the nano catalytic composite materials. The nano catalytic composite materials prepared by the method have stable structure, uniform nano catalyst dispersion and controllable particle diameter and appearance.
Description
Technical field
The present invention relates to a kind of preparation method of nano catalytic composite materials, particularly relate to the preparation method that a kind of ultrasonic wave-film-anti-solvent method integrating process prepares nano catalytic composite materials (nanocatalyst/ammoniumper chlorate matrix material).
Background technology
Ammoniumper chlorate is that solid propellant is a kind of with the solid propellant of ammoniumper chlorate as oxygenant, and it is a kind of important energetic material, has consequence in a plurality of fields such as guided missile and spationauticies.In order to improve the combustionproperty that ammoniumper chlorate is a solid propellant, use nanocatalyst to be proved to be a kind of efficient ways.But, how nanocatalyst is disperseed to be subjected to better investigator's concern because nanoparticle easily reunites.
Being used to solve the method that propelling agent reunites with nanocatalyst and oxygenant at present mainly is surface-modification method.Carry out modification with tensio-active agent, organic acid and macromolecular material, can improve the dispersiveness of nanocatalyst and ultra-fine oxygenant to a certain extent.But because surface modification is not really assembled on molecular level, it is dispersed and unsatisfactory propelling agent.And the surface modification agent material that uses in modifying process is not the propellant formulation composition, and this not only can reduce the energy characteristics of propelling agent relatively, and may influence the consistency between other component of catalyzer, oxygenant and propelling agent.Thereby under the condition of not introducing non-propellant formulation composition, the dispersiveness that effectively improves nanocatalyst and ultra-fine oxygenant is to improve the key point of propellant performance.With the direct compound preparation matrix material of the principal constituent of propelling agent, be proved to be one of important method that obtains by the high-performance propelling agent.
Anti-solvent method is the important method that preparation has the nanocatalyst/ammoniumper chlorate composite particles of nucleocapsid structure.Its process is the anti-solvent that has added precipitate in the saturated solution of precipitate, makes it reach supersaturation and separates out.Its marrow is nucleation and the growth of controlling particle by the degree of supersaturation of regulator solution.Conventional anti-solvent method has two problems to need to solve: (1) conventional mechanical stirring is difficult to nano material is distributed in the non-solvent equably, and the homodisperse of nano material in non-solvent is to prepare the prerequisite of all disperseing nano catalytic composite materials.(2) ordinary method is difficult to control accurately the degree of supersaturation and the diffusion of solution, thereby is difficult to obtain particle diameter and the controlled nano catalytic composite materials of pattern.
The dispersion of patent CN 1114634C using ultrasound ripple, pulverizing, activation cause multiple action and prepare Stability Analysis of Structures, the finely dispersed polymer/inorganic nanometer particle composite material of inorganic nano-particle.The disclosed ceramic film antisolvent coupling process in semi-continuous type that utilizes prepares particle diameter and the controlled superfine powder of pattern among the patent CN 101474492A.But in the process of preparation nano composite material, all dispersion problem of nano material in anti-solvent cannot solve.
Summary of the invention:
The purpose of this invention is to provide a kind of ultrasonic wave-film-anti-solvent method integrating process that utilizes and prepare the method for the controlled nano catalytic composite materials of nanoparticle good dispersity, structure and pattern.Utilize hyperacoustic ultra-sonic dispersion effect, can guarantee the homodisperse of nanoparticle in anti-solvent.Utilize the evenly reinforced and dissemination of film pipe, can control the degree of supersaturation of reaction effectively, make the controlled nano-complex particle of particle diameter and pattern.
Technical scheme of the present invention is: a kind of ultrasonic wave-film-anti-solvent method integrating process prepares the preparation method of nano catalytic composite materials (nanocatalyst/ammoniumper chlorate matrix material), and concrete step is:
(1), ammoniumper chlorate saturated solution preparation process: at a certain temperature, ammoniumper chlorate is dissolved in the suitable solvent makes saturated solution;
(2), nanocatalyst dispersion process: at a certain temperature, under action of ultrasonic waves, nanocatalyst is dispersed in the anti-solvent;
(3), preparation process: under certain pressure, the logical filmed passing tube of the saturated solution of ammoniumper chlorate is added in the anti-solvent; Under action of ultrasonic waves, anti-solvent with solvent anti-molten after, ammoniumper chlorate will be separated out, and is coated on the surface of homodisperse catalyst nanoparticles, forms nano catalytic composite materials;
(4), filtration drying process: above-mentioned nano-complex particle is carried out solid-liquid separation by ceramic-film tube earlier;
(5), the material after separating in 50～150 ℃ carry out drying after, obtain nano catalytic composite materials.
Wherein said nanocatalyst is a nano inorganic material, comprises that nano-metal-oxide is (as Fe
2O
3, CuO, Co
2O
3), Nano metal powder (as Ni, Cu, A1), composite oxides and composite metal powder etc., size is 10～200nm.
Wherein selected porous-film is organic membrane or the mineral membrane of aperture 5～1500nm in the step (3), and preferred porous-film aperture is the mineral membrane of 50～800nm.
Wherein in step (1) and the step (2), the material that can dissolve ammoniumper chlorate at a certain temperature can be elected to be the solvent of ammoniumper chlorate; Insoluble ammoniumper chlorate or the ammoniumper chlorate material that solubleness is very little therein is optional as anti-solvent; Solvent and the anti-solvent selected can dissolve each other; The solvent of ammoniumper chlorate and the pairing of non-solvent can be: water-ethanol, acetone-ethyl acetate, DMF-ethyl acetate.
Wherein the certain temperature described in the step (1) is meant between the zero pour of solvent and the temperature between the boiling point.Certain temperature described in the step (2) is meant between the zero pour of non-solvent and the temperature between the boiling point.
Wherein in step (2) and the step (3), ultrasonic power: 50～1500w, ultrasonic frequency is: 2 * 10
4～10
9Hz, ultrasonic time are 5～60min.
Wherein in the step (3), the ratio of solvent and anti-solvent is 1: 3～1: 20.
Wherein in the step (3), the pressure that is adopted is 0.1～1MPa.
Wherein in the step (4), 50～150 ℃ of drying temperatures, time of drying 1～5h.
Beneficial effect of the present invention:
1. the present invention is before nanocatalyst coats, and using ultrasound wave radiation technology is dispersed in nanocatalyst in the anti-solvent, provides the guarantor to levy for obtaining the homodisperse of nanocatalyst in matrix material.
2. the present invention utilizes the film pipe to carry out controlled feeding in raw material, utilize the dissemination of the reinforced even and film pipe of film pipe, can control the degree of supersaturation of solution effectively, thereby obtain Stability Analysis of Structures, nanocatalyst is uniformly dispersed and particle diameter and the controlled nano catalytic composite materials of pattern.
3. the present invention is with ultrasonic wave, film pipe and the coupling of anti-solvent method, and the preparation method has low, the characteristic of simple process of production cost.The nano catalytic composite materials that adopts the present invention's preparation is controlled through particle diameter and pattern that HRTEM and SEM characterize nano catalytic composite materials as can be known.
Description of drawings
Fig. 1 is a nanometer Fe
2O
3The HRTEM photo of/AP catalytic composite materials;
Fig. 2 is a nanometer Fe
2O
3The SEM photo of/AP catalytic composite materials.
Fig. 3 is a nanometer Fe
2O
3Carry out simple blended SEM photo with AP.
Further specify the performance of the inventive method and nano catalytic composite materials below by embodiment and Comparative Examples.
Embodiment
Embodiment 1, nanometer Fe
2O
3The preparation of/AP catalytic composite materials
At first (ultrasonic power is 1000w, and ultrasonic frequency is 10 under the ultrasonic wave effect
6Hz, ultrasonic time are 15min), with certain amount of nano Fe
2O
3(30nm) be dispersed in the 200mL ethyl acetate.Then under the effect of 0.3MPa nitrogen, the saturated acetone soln of AP of 20mL is pressed in the crystallizer, then AP will be with nanometer Fe
2O
3For nuclear, form nanometer Fe at last in its surface growth
2O
3/ AP composite particles.After the nano composite material that makes filtered, washs, at 60 ℃ of following vacuum-drying 3h.
Embodiment 2, the preparation of nanometer CuO/AP catalytic composite materials
At first (ultrasonic power is 1200w, and ultrasonic frequency is 10 under the ultrasonic wave effect
7Hz, ultrasonic time are 20min), certain amount of nano CuO is dispersed in the 300mL ethyl acetate.Then under the effect of 0.4MPa nitrogen, the saturated DMF solution of AP of 10mL is pressed in the crystallizer, then AP will be a nuclear with nanometer CuO, forms nanometer CuO/AP composite particles at last in its surface growth.After the nano composite material that makes filtered, washs, at 60 ℃ of following vacuum-drying 3h.
Embodiment 3, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is Co
2O
3Described nanocatalyst size is 10nm.
The solvent of described ammoniumper chlorate selects water; The non-solvent of described ammoniumper chlorate selects ethanol.
Embodiment 4, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is Nano metal powder Ni; Described nanocatalyst size is 10nm.
The solvent of described ammoniumper chlorate is selected acetone; The non-solvent of described ammoniumper chlorate is selected ethyl acetate.
Embodiment 5, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is Nano metal powder Cu; Described nanocatalyst size is 5nm.
The solvent of described ammoniumper chlorate is DMF; The non-solvent of described ammoniumper chlorate is selected ethyl acetate.
Embodiment 6, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is the Nano metal powder of Al; Described nanocatalyst size is 100nm.
Embodiment 7, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is Fe
2O
3, CuO and Co
2O
3The composite nano oxide powder.
Embodiment 8, and is substantially the same manner as Example 1, but following change is arranged:
Described nanocatalyst is the composite Nano metal powder of Ni, Cu and Al.
Claims (10)
1. one kind is utilized ultrasonic wave-film-anti-solvent method integrating process to prepare the method for nano catalytic composite materials, it is characterized in that: step is as follows:
(1) the saturated solution preparation process of ammoniumper chlorate: at a certain temperature, ammoniumper chlorate is dissolved in the suitable solvent makes saturated solution;
(2) nanocatalyst dispersion process: at a certain temperature, under action of ultrasonic waves, nanocatalyst is dispersed in the anti-solvent;
(3) preparation process: under certain pressure, the logical filmed passing tube of the saturated solution of ammoniumper chlorate is added in the non-solvent; Under action of ultrasonic waves, anti-solvent with solvent anti-molten after, ammoniumper chlorate will be separated out, and is coated on the surface of homodisperse nanoparticle, forms nano catalytic composite materials;
(4), filtration drying process: above-mentioned nano-complex particle is carried out solid-liquid separation by ceramic-film tube earlier;
(5), the material after separating in 50～150 ℃ carry out drying after, obtain nano catalytic composite materials.
2. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that, described nanocatalyst is a nano inorganic material, is selected from: nano-metal-oxide, Nano metal powder, composite oxides or composite metal powder.
3. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 2 prepares the method for nano catalytic composite materials, it is characterized in that described nano-metal-oxide is selected from: Fe
2O
3, CuO or Co
2O
3Described Nano metal powder is selected from: Ni, Cu or A1; Described nanocatalyst size is 10～200nm.
4. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that the nanocatalyst size is 5～100nm.
5. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that, the solvent of described ammoniumper chlorate and the pairing of non-solvent are: water-ethanol, acetone-ethyl acetate, DMF-ethyl acetate.
6. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that, selected porous-film is organic membrane or the mineral membrane of aperture 5～1500nm.
7. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 6 prepares the method for nano catalytic composite materials, it is characterized in that, selected porous-film is that the aperture is the mineral membrane of 50～800nm.
8. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that, ultrasonic power is 50～1500w in step (2) and (3), and ultrasonic frequency is 2 * 10
4～10
9Hz, ultrasonic time are 5～60min.
9. ultrasonic wave-film-anti-solvent method the integrating process that utilizes according to claim 1 prepares the method for nano catalytic composite materials, it is characterized in that described solvent and anti-solvent, the volume ratio of solvent and anti-solvent are 1: 3～1: 30.
10. prepare the method for nano catalytic composite materials according to the described ultrasonic wave-film-anti-solvent method integrating process that utilizes of one of claim 1～9, it is characterized in that the certain temperature described in the step (1) is meant between the zero pour of the solvent that is selected as AP and the temperature between the boiling point; Certain temperature described in the step (2) is meant between the zero pour of the non-solvent that is selected as AP and the temperature between the boiling point; The pressure that adopts in the step (3) is 0.1～1MPa; Drying temperature is 50～150 ℃ in the step (4), and be 1～5h time of drying.
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Cited By (12)
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|---|---|---|---|---|
| CN102320903A (en) * | 2011-06-16 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102515984A (en) * | 2011-10-14 | 2012-06-27 | 华中科技大学 | Core-shell nano-composite material and its preparation method |
| CN102718187A (en) * | 2012-07-02 | 2012-10-10 | 南京师范大学 | Hollow ultrafine ammonium perchlorate and preparation method thereof |
| CN103055958A (en) * | 2012-12-03 | 2013-04-24 | 华中科技大学 | Method for coating nano metal oxide catalyst precursor on ammonium perchlorate surface |
| CN103086815A (en) * | 2013-01-31 | 2013-05-08 | 陕西师范大学 | Preparation method for styrene-coated ammonium perchlorate |
| CN105665718A (en) * | 2016-02-01 | 2016-06-15 | 南京师范大学 | Preparation method of nano aluminum/ammonium perchlorate (Al/AP) energy-containing composite particles |
| CN105689724A (en) * | 2016-02-01 | 2016-06-22 | 南京师范大学 | Preparing method of nano Al/CuO-AP energy-contained composite particles |
| CN106365934A (en) * | 2016-08-25 | 2017-02-01 | 中国工程物理研究院化工材料研究所 | Preparation method of AP/Ni/Al composite material |
| CN115925500A (en) * | 2022-05-25 | 2023-04-07 | 南京理工大学 | Solid propellant and preparation method thereof |
| CN115947640A (en) * | 2023-01-31 | 2023-04-11 | 南京师范大学 | Aluminum powder/fluoropolymer/ammonium perchlorate energetic composite particle and preparation method thereof |
| CN116040674A (en) * | 2023-02-08 | 2023-05-02 | 成都理工大学 | Surface coating technology of inorganic powder material with high efficiency and low cost |
| CN116553987A (en) * | 2023-06-27 | 2023-08-08 | 哈尔滨工业大学 | Method for preparing zirconium hydride coated ammonium perchlorate composite energetic material through solvent anti-solvent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201431800Y (en) * | 2008-12-19 | 2010-03-31 | 南京工业大学 | Device for preparing and concentrating ultra-fine powder by coupling of membrane tube and anti-solvent method |
-
2010
- 2010-06-10 CN CN2010101980738A patent/CN101863725B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201431800Y (en) * | 2008-12-19 | 2010-03-31 | 南京工业大学 | Device for preparing and concentrating ultra-fine powder by coupling of membrane tube and anti-solvent method |
Non-Patent Citations (1)
| Title |
|---|
| 《固体火箭技术》 20040625 陈爱四等 "纳米CuO/AP复合粒子的制备及催化性能研究" 第2，3节 1-10 第27卷, 第2期 2 * |
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| CN102320903A (en) * | 2011-06-16 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102320903B (en) * | 2011-06-16 | 2013-11-06 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102515984A (en) * | 2011-10-14 | 2012-06-27 | 华中科技大学 | Core-shell nano-composite material and its preparation method |
| CN102515984B (en) * | 2011-10-14 | 2013-12-25 | 华中科技大学 | Core-shell nano-composite material and its preparation method |
| CN102718187A (en) * | 2012-07-02 | 2012-10-10 | 南京师范大学 | Hollow ultrafine ammonium perchlorate and preparation method thereof |
| CN103055958A (en) * | 2012-12-03 | 2013-04-24 | 华中科技大学 | Method for coating nano metal oxide catalyst precursor on ammonium perchlorate surface |
| CN103086815A (en) * | 2013-01-31 | 2013-05-08 | 陕西师范大学 | Preparation method for styrene-coated ammonium perchlorate |
| CN103086815B (en) * | 2013-01-31 | 2014-11-05 | 陕西师范大学 | Preparation method for styrene-coated ammonium perchlorate |
| CN105665718A (en) * | 2016-02-01 | 2016-06-15 | 南京师范大学 | Preparation method of nano aluminum/ammonium perchlorate (Al/AP) energy-containing composite particles |
| CN105689724A (en) * | 2016-02-01 | 2016-06-22 | 南京师范大学 | Preparing method of nano Al/CuO-AP energy-contained composite particles |
| CN105689724B (en) * | 2016-02-01 | 2018-01-05 | 南京师范大学 | A kind of preparation method of nanometer of Al/CuO AP compound particles containing energy |
| CN106365934A (en) * | 2016-08-25 | 2017-02-01 | 中国工程物理研究院化工材料研究所 | Preparation method of AP/Ni/Al composite material |
| CN106365934B (en) * | 2016-08-25 | 2018-08-14 | 中国工程物理研究院化工材料研究所 | A kind of preparation method of AP/Ni/Al composite materials |
| CN115925500A (en) * | 2022-05-25 | 2023-04-07 | 南京理工大学 | Solid propellant and preparation method thereof |
| CN115947640A (en) * | 2023-01-31 | 2023-04-11 | 南京师范大学 | Aluminum powder/fluoropolymer/ammonium perchlorate energetic composite particle and preparation method thereof |
| CN116040674A (en) * | 2023-02-08 | 2023-05-02 | 成都理工大学 | Surface coating technology of inorganic powder material with high efficiency and low cost |
| CN116553987A (en) * | 2023-06-27 | 2023-08-08 | 哈尔滨工业大学 | Method for preparing zirconium hydride coated ammonium perchlorate composite energetic material through solvent anti-solvent |
| CN116553987B (en) * | 2023-06-27 | 2024-03-12 | 哈尔滨工业大学 | Method for preparing zirconium hydride coated ammonium perchlorate composite energetic material through solvent anti-solvent |
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