CN101863725B - 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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- CN101863725B CN101863725B CN2010101980738A CN201010198073A CN101863725B CN 101863725 B CN101863725 B CN 101863725B CN 2010101980738 A CN2010101980738 A CN 2010101980738A CN 201010198073 A CN201010198073 A CN 201010198073A CN 101863725 B CN101863725 B CN 101863725B
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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/ammonium perchlorate composite).
Background technology
Ammonium perchlorate is that solid propellant is a kind of with the solid propellant of ammonium perchlorate as oxidant, and it is a kind of important energetic material, has consequence in a plurality of fields such as guided missile and space technologies.In order to improve the combustibility that ammonium perchlorate is a solid propellant, use nanocatalyst to be proved to be a kind of efficient ways.But, how nanocatalyst is disperseed to receive researcher's concern better because nano particle is prone to reunite.
Being used to solve the method that propellant reunites with nanocatalyst and oxidant at present mainly is surface-modification method.Carry out modification with surfactant, organic acid and macromolecular material, can improve the dispersiveness of nanocatalyst and ultra-fine oxidant to a certain extent.But because surface modification is not really assembled on molecular level, it is dispersed and unsatisfactory propellant.And the surface modification agent material that in modifying process, uses is not the propellant formulation composition, and this not only can reduce the energy characteristics of propellant relatively, and may influence the compatibility between other component of catalyst, oxidant and propellant.Thereby under the condition of not introducing non-propellant formulation composition, the dispersiveness that effectively improves nanocatalyst and ultra-fine oxidant is to improve the key point of the performance of propellant.With the direct compound preparation composite of the principal component of propellant, be proved to be one of important method that obtains by the high-performance propellant.
Anti-solvent method is the important method that preparation has the nanocatalyst/ammonium perchlorate compound particle of nucleocapsid structure.Its process is the anti-solvent that in the saturated solution of precipitate, has added precipitate, makes it reach supersaturation and separates out.Its marrow is nucleation and the growth of controlling particle through the degree of supersaturation of regulator solution.Conventional anti-solvent method has two problems to need to solve: (1) conventional mechanical agitation is difficult to be distributed to nano material in the non-solvent equably, and the even dispersion of nano material in non-solvent is to prepare the prerequisite of all disperseing nano catalytic composite materials.(2) conventional 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 nano particle good dispersion, structure and pattern.Utilize hyperacoustic ultrasonic peptizaiton, can guarantee the even dispersion of nano particle in anti-solvent.Utilize the evenly reinforced and peptizaiton 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/ammonium perchlorate composite), and concrete step is:
(1), the ammonium perchlorate saturated solution prepares process: at a certain temperature, ammonium perchlorate is dissolved in the suitable solvent processes 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 ammonium perchlorate is added in the anti-solvent; Under action of ultrasonic waves, after anti-solvent instead dissolved solvent, ammonium perchlorate 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 Separation of Solid and Liquid through 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 (like Fe
2O
3, CuO, Co
2O
3), Nano metal powder (like Ni, Cu, A1), composite oxides and composite metal powder etc., size is 10～200nm.
The perforated membrane of wherein being selected for use in the step (3) is organic film or the inoranic membrane of aperture 5～1500nm, and preferred perforated membrane aperture is the inoranic membrane of 50～800nm.
Wherein in step (1) and the step (2), the material that can dissolve ammonium perchlorate at a certain temperature can be elected to be the solvent of ammonium perchlorate; Insoluble ammonium perchlorate or the ammonium perchlorate material that solubility is very little therein is optional as anti-solvent; Solvent and the anti-solvent selected can dissolve each other; The solvent of ammonium perchlorate and the pairing of non-solvent can be: water-ethanol, acetone-ethyl acetate, DMF-ethyl acetate.
Wherein the uniform temperature described in the step (1) is meant between the freezing point of solvent and the temperature between the boiling point.Uniform temperature described in the step (2) is meant between the freezing point of non-solvent and the temperature between the boiling point.
Wherein in step (2) and the step (3), ultrasonic power: 50～1500w, supersonic 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 baking temperatures, drying time 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 even dispersion of nanocatalyst in composite.
2. the present invention utilizes the film pipe to carry out controlled feeding in raw material; Utilize the peptizaiton 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 can know that through HRTEM and SEM sign the particle diameter of nano catalytic composite materials and pattern are controlled.
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
3The SEM photo that simply mixes with AP.
Further specify the performance of the inventive method and nano catalytic composite materials below through embodiment and Comparative Examples.
The specific embodiment
Embodiment 1, nanometer Fe
2O
3The preparation of/AP catalytic composite materials
At first (ultrasonic power is 1000w, and supersonic 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 crystallizing tank, then AP will be with nanometer Fe
2O
3For nuclear, form nanometer Fe at last in its superficial growth
2O
3/ AP compound particle.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 supersonic 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 crystallizing tank, then AP will be a nuclear with nanometer CuO, forms nanometer CuO/AP compound particle at last in its superficial growth.After the nano composite material that makes filtered, washs, at 60 ℃ of following vacuum drying 3h.
Embodiment 3, and is basic identical with embodiment 1, but following change is arranged:
Described nanocatalyst is Co
2O
3Described nanocatalyst size is 10nm.
The solvent of described ammonium perchlorate selects water; The non-solvent of described ammonium perchlorate selects ethanol.
Embodiment 4, and is basic identical with embodiment 1, but following change is arranged:
Described nanocatalyst is Nano metal powder Ni; Described nanocatalyst size is 10nm.
The solvent of described ammonium perchlorate is selected acetone; The non-solvent of described ammonium perchlorate is selected ethyl acetate.
Embodiment 5, and is basic identical with embodiment 1, but following change is arranged:
Described nanocatalyst is Nano metal powder Cu; Described nanocatalyst size is 5nm.
The solvent of described ammonium perchlorate is DMF; The non-solvent of described ammonium perchlorate is selected ethyl acetate.
Embodiment 6, and is basic identical with embodiment 1, but following change is arranged:
Described nanocatalyst is the Nano metal powder of Al; Described nanocatalyst size is 100nm.
Embodiment 7, and is basic identical with embodiment 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 basic identical with embodiment 1, but following change is arranged:
Described nanocatalyst is the composite Nano metal powder of Ni, Cu and Al.
Claims (4)
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 following:
(1) saturated solution of ammonium perchlorate prepares process: at a certain temperature, ammonium perchlorate is dissolved in the suitable solvent processes 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 ammonium perchlorate is added in the anti-solvent; Under action of ultrasonic waves, after anti-solvent instead dissolved solvent, ammonium perchlorate will be separated out, and is coated on the surface of homodisperse nanocatalyst, forms nano-complex particle;
(4), filtration drying process: above-mentioned nano-complex particle is carried out Separation of Solid and Liquid through ceramic-film tube earlier; Material after the separation in 50～150 ℃ carry out drying after, obtain nano catalytic composite materials;
Described nanocatalyst is nano-metal-oxide or Nano metal powder;
The solvent of described ammonium perchlorate and the pairing of anti-solvent are: water-ethanol, acetone-ethyl acetate, DMF-ethyl acetate;
Uniform temperature described in the step (1) is meant between the freezing point of the solvent that is selected as ammonium perchlorate and the temperature between the boiling point; Uniform temperature described in the step (2) is meant between the freezing point of the anti-solvent that is selected as ammonium perchlorate and the temperature between the boiling point; The pressure that adopts in the step (3) is 0.1～1MPa; Baking temperature is 50～150 ℃ in the step (4), and be 1～5h drying time.
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 nano-metal-oxide is Fe
2O
3, CuO or Co
2O
3Described Nano metal powder is Ni, Cu or Al; Described nanocatalyst size is 10～200nm.
3. 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 supersonic frequency is 2 * 10
4～10
9Hz, ultrasonic time are 5～60min.
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 volume ratio of said solvent and anti-solvent is 1: 3～1: 30.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102515984B (en) * | 2011-10-14 | 2013-12-25 | 华中科技大学 | Core-shell nano-composite material and its preparation method |
| CN102718187B (en) * | 2012-07-02 | 2014-03-26 | 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 |
| 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 |
| 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 |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 (2)
| Title |
|---|
| 陈爱四等."纳米CuO/AP复合粒子的制备及催化性能研究".《固体火箭技术》.2004,第27卷(第2期),第2，3节. |
| 陈爱四等."纳米CuO/AP复合粒子的制备及催化性能研究".《固体火箭技术》.2004,第27卷(第2期),第2,3节. * |
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