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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Abstract
Description
技术领域 technical field
本发明涉及一种纳米催化复合材料的制备方法，特别是涉及一种超声波-膜-反溶剂法集成过程制备纳米催化复合材料(纳米催化剂/高氯酸铵复合材料)的制备方法。The invention relates to a preparation method of a nano catalytic composite material, in particular to a preparation method for preparing a nano catalytic composite material (nano catalyst/ammonium perchlorate composite material) through an integrated process of an ultrasonic-membrane-antisolvent method.
背景技术 Background technique
高氯酸铵系固体推进剂是一种以高氯酸铵作为氧化剂的固体推进剂，它是一种重要的含能材料，在导弹和航天技术等多个领域具有重要的地位。为了提高高氯酸铵系固体推进剂的燃烧性能，使用纳米催化剂被证明是一种行之有效的方法。但由于纳米粒子易团聚的特点，如何将纳米催化剂更好地分散受到研究者的关注。Ammonium perchlorate-based solid propellant is a solid propellant that uses ammonium perchlorate as an oxidant. It is an important energetic material and plays an important role in many fields such as missile and aerospace technology. In order to improve the combustion performance of ammonium perchlorate-based solid propellants, the use of nano-catalysts has been proven to be an effective method. However, due to the characteristics of easy aggregation of nanoparticles, how to better disperse nanocatalysts has attracted the attention of researchers.
目前用于解决推进剂用纳米催化剂和氧化剂团聚的方法主要是表面改性法。用表面活性剂、有机酸和高分子材料进行改性，可在一定程度上提高纳米催化剂和超细氧化剂的分散性。但由于表面改性并未真正在分子水平上进行组装，其在推进剂的分散性并不尽人意。而且在改性过程中使用的表面改性剂材料不是推进剂配方成分，这不仅会相对降低推进剂的能量性能，而且可能会影响催化剂、氧化剂与推进剂其它组分之间的相容性。因而，在不引入非推进剂配方成分的条件下，有效提高纳米催化剂和超细氧化剂的分散性是提高推进剂性能的关键所在。将推进剂的主成分直接复合制备复合材料，被证明是获得高性能推进剂的重要方法之一。The current method used to solve the agglomeration of nano-catalysts and oxidants used in propellants is mainly surface modification. Modification with surfactants, organic acids and polymer materials can improve the dispersion of nano-catalysts and ultra-fine oxidants to a certain extent. However, its dispersibility in propellants is not satisfactory because the surface modification does not really assemble at the molecular level. Moreover, the surface modifier material used in the modification process is not a component of the propellant formulation, which will not only relatively reduce the energy performance of the propellant, but may also affect the compatibility between catalysts, oxidizers and other components of the propellant. Therefore, effectively improving the dispersion of nanocatalysts and ultrafine oxidizers is the key to improving the performance of propellants without introducing non-propellant formulation components. It has been proved to be one of the important methods to obtain high-performance propellants by directly compounding the main components of propellants to prepare composite materials.
反溶剂法是制备具有核-壳结构的纳米催化剂/高氯酸铵复合粒子的重要方法。其过程是在析出物的饱和溶液中加入了析出物的反溶剂，使其达到过饱和而析出。其精髓是通过调节溶液的过饱和度来控制粒子的成核和生长。常规的反溶剂法有两个问题需要解决：(1)常规的机械搅拌很难把纳米材料均匀地分散到非溶剂中，而纳米材料在非溶剂中的均匀分散是制备均分散纳米催化复合材料的前提。(2)常规方法很难精准地控制溶液的过饱和度和扩散程度，从而很难得到粒径和形貌可控的纳米催化复合材料。Anti-solvent method is an important method to prepare nanocatalyst/ammonium perchlorate composite particles with core-shell structure. The process is that the anti-solvent of the precipitate is added to the saturated solution of the precipitate to make it supersaturated and precipitate. Its essence is to control the nucleation and growth of particles by adjusting the supersaturation of the solution. The conventional anti-solvent method has two problems to be solved: (1) It is difficult to uniformly disperse the nanomaterials into the non-solvent by conventional mechanical stirring, and the uniform dispersion of the nanomaterials in the non-solvent is the key to prepare homogeneously dispersed nanocatalytic composite materials. premise. (2) It is difficult to precisely control the supersaturation and diffusion degree of the solution by conventional methods, so it is difficult to obtain nano-catalytic composite materials with controllable particle size and morphology.
专利CN 1114634C应用超声波的分散、粉碎、活化引发多重作用制备结构稳定、无机纳米粒子分散均匀的聚合物/无机纳米粒子复合材料。专利CN 101474492A中公开的利用陶瓷膜反溶剂耦合过程半连续式制备粒径和形貌可控的超细粉体。但在制备纳米复合材料的过程中，纳米材料在反溶剂中的均分散问题没法解决。Patent CN 1114634C uses ultrasonic dispersion, crushing, and activation to trigger multiple actions to prepare a polymer/inorganic nanoparticle composite material with stable structure and uniform dispersion of inorganic nanoparticles. Patent CN 101474492A discloses semi-continuous preparation of ultrafine powder with controllable particle size and shape by using ceramic membrane anti-solvent coupling process. However, in the process of preparing nanocomposites, the uniform dispersion of nanomaterials in antisolvent cannot be solved.
发明内容：Invention content:
本发明的目的是提供一种利用超声波-膜-反溶剂法集成过程制备纳米粒子分散性好、结构和形貌可控的纳米催化复合材料的方法。利用超声波的超声分散作用，可保证纳米粒子在反溶剂中的均匀分散。利用膜管的均匀加料以及分散作用，可以有效地控制反应的过饱和度，制得粒径和形貌可控的纳米复合粒子。The purpose of the present invention is to provide a method for preparing nano-catalyzed composite materials with good dispersion of nanoparticles and controllable structure and morphology by using the integrated process of ultrasonic-membrane-anti-solvent method. Utilizing the ultrasonic dispersion effect of ultrasonic waves can ensure the uniform dispersion of nanoparticles in the anti-solvent. Utilizing the uniform feeding and dispersion of the membrane tube, the supersaturation of the reaction can be effectively controlled, and nanocomposite particles with controllable particle size and shape can be prepared.
本发明的技术方案为：一种超声波-膜-反溶剂法集成过程制备纳米催化复合材料(纳米催化剂/高氯酸铵复合材料)的制备方法，具体的步骤为：The technical scheme of the present invention is: a kind of preparation method of nano catalytic composite material (nano catalyst/ammonium perchlorate composite material) in the integrated process of ultrasonic-membrane-antisolvent method, concrete steps are:
(1)、高氯酸铵饱和溶液制备过程：在一定温度下，将高氯酸铵溶解在合适的溶剂中制成饱和溶液；(1), ammonium perchlorate saturated solution preparation process: at a certain temperature, ammonium perchlorate is dissolved in a suitable solvent to make a saturated solution;
(2)、纳米催化剂分散过程：在一定温度下，在超声波的作用下，将纳米催化剂均匀分散在反溶剂中；(2) Nano-catalyst dispersion process: at a certain temperature, under the action of ultrasonic waves, the nano-catalyst is evenly dispersed in the anti-solvent;
(3)、制备过程：在一定的压力下，将高氯酸铵的饱和溶液通过膜管加到反溶剂中；在超声波的作用下，反溶剂将溶剂反溶后，高氯酸铵将会析出，包覆在均匀分散的催化剂纳米粒子的表面，形成纳米催化复合材料；(3), preparation process: under certain pressure, the saturated solution of ammonium perchlorate is added in the anti-solvent through film tube; Precipitation, coating on the surface of uniformly dispersed catalyst nanoparticles to form nano-catalytic composite materials;
(4)、过滤干燥过程：将上述的纳米复合粒子先通过陶瓷膜管进行固液分离；(4) Filtration and drying process: the above-mentioned nanocomposite particles are first separated from the solid and liquid through the ceramic membrane tube;
(5)、分离后的材料于50～150℃进行干燥后，得到纳米催化复合材料。(5) After the separated material is dried at 50-150° C., a nano catalytic composite material is obtained.
其中所述的纳米催化剂为纳米无机材料，包括纳米金属氧化物(如Fe2O3、CuO、Co2O3)、纳米金属粉(如Ni、Cu、A1)、复合氧化物以及复合金属粉等，粒径大小为10～200nm。The nano-catalysts described therein are nano-inorganic materials, including nano-metal oxides (such as Fe 2 O 3 , CuO, Co 2 O 3 ), nano-metal powders (such as Ni, Cu, Al), composite oxides, and composite metal powders. etc., the particle size is 10-200nm.
其中步骤(3)中所选用的多孔膜为孔径5～1500nm的有机膜或无机膜，优选多孔膜孔径为50～800nm的无机膜。Wherein the porous membrane selected in step (3) is an organic or inorganic membrane with a pore diameter of 5-1500 nm, preferably an inorganic membrane with a pore diameter of 50-800 nm.
其中步骤(1)和步骤(2)中，能在一定温度下溶解高氯酸铵的物质可选作高氯酸铵的溶剂；不溶高氯酸铵或高氯酸铵在其中溶解度很小的物质可选作为反溶剂；选择的溶剂和反溶剂能互溶；高氯酸铵的溶剂与非溶剂的配对可以是：水-乙醇，丙酮-乙酸乙酯、DMF-乙酸乙酯。Wherein in step (1) and step (2), the material that can dissolve ammonium perchlorate at a certain temperature can be selected as the solvent of ammonium perchlorate; Insoluble ammonium perchlorate or ammonium perchlorate solubility is very little therein The substance can be selected as anti-solvent; the selected solvent and anti-solvent can be miscible; the pairing of ammonium perchlorate solvent and non-solvent can be: water-ethanol, acetone-ethyl acetate, DMF-ethyl acetate.
其中步骤(1)中所述的一定温度是指介于溶剂的凝固点和沸点之间的温度。步骤(2)中所述的一定温度是指介于非溶剂的凝固点和沸点之间的温度。Wherein the certain temperature described in the step (1) refers to the temperature between the freezing point and the boiling point of the solvent. The certain temperature described in step (2) refers to the temperature between the freezing point and the boiling point of the non-solvent.
其中步骤(2)和步骤(3)中，超声功率：50～1500w，超声频率为：2×104～109Hz，超声时间为5～60min。Wherein in step (2) and step (3), ultrasonic power: 50-1500w, ultrasonic frequency: 2×10 4 -10 9 Hz, ultrasonic time: 5-60 min.
其中步骤(3)中，溶剂与反溶剂的比例为1∶3～1∶20。Wherein in step (3), the ratio of solvent to anti-solvent is 1:3-1:20.
其中步骤(3)中，所采用的压力为0.1～1MPa。Wherein in step (3), the pressure adopted is 0.1～1MPa.
其中步骤(4)中，干燥温度50～150℃，干燥时间1～5h。Wherein in step (4), the drying temperature is 50-150° C., and the drying time is 1-5 hours.
本发明的有益效果：Beneficial effects of the present invention:
1.本发明在纳米催化剂进行包覆前，应用超声波辐射技术将纳米催化剂均匀分散在反溶剂中，为获得纳米催化剂在复合材料中的均匀分散提供了保征。1. The present invention uses ultrasonic radiation technology to uniformly disperse the nano-catalyst in the anti-solvent before the nano-catalyst is coated, which provides a guarantee for obtaining the uniform dispersion of the nano-catalyst in the composite material.
2.本发明利用膜管进行可控加料，利用膜管加料的均匀以及膜管的分散作用，可以有效地控制溶液的过饱和度，从而得到结构稳定、纳米催化剂分散均匀以及粒径和形貌可控的纳米催化复合材料。2. The present invention uses the membrane tube to carry out controllable feeding, and utilizes the uniform feeding of the membrane tube and the dispersing effect of the membrane tube to effectively control the supersaturation of the solution, thereby obtaining stable structure, uniform dispersion of nano-catalysts, and particle size and morphology Controllable nanocatalytic composites.
3.本发明将超声波、膜管和反溶剂法耦合，制备方法具有生产成本低、工艺过程简单的特点。采用本发明制备的纳米催化复合材料经HRTEM和SEM表征可知纳米催化复合材料的粒径和形貌可控。3. The present invention couples ultrasonic wave, membrane tube and anti-solvent method, and the preparation method has the characteristics of low production cost and simple process. The HRTEM and SEM characterization of the nano catalytic composite material prepared by the invention shows that the particle size and shape of the nano catalytic composite material are controllable.
附图说明 Description of drawings
图1为纳米Fe2O3/AP催化复合材料的HRTEM照片；Figure 1 is the HRTEM photo of the nano-Fe 2 O 3 /AP catalytic composite;
图2为纳米Fe2O3/AP催化复合材料的SEM照片。Fig. 2 is the SEM photograph of the nanometer Fe 2 O 3 /AP catalytic composite material.
图3为纳米Fe2O3和AP进行简单混合的SEM照片。Figure 3 is the SEM photo of simple mixing of nano Fe 2 O 3 and AP.
下面通过实施例和对比例进一步说明本发明方法和纳米催化复合材料的性能。The following examples and comparative examples further illustrate the performance of the method of the present invention and the nano-catalytic composite material.
具体实施方式 Detailed ways
实施例1，纳米Fe2O3/AP催化复合材料的制备Embodiment 1, the preparation of nano Fe 2 O 3 /AP catalytic composite material
首先在超声波作用下(超声功率为1000w，超声频率为106Hz，超声时间为15min)，将一定量的纳米Fe2O3(30nm)分散在200mL乙酸乙酯中。然后在0.3MPa氮气的作用下，将20mL的AP饱和丙酮溶液压入结晶罐中，则AP将会以纳米Fe2O3为核，在其表面生长最后形成纳米Fe2O3/AP复合粒子。将制得的纳米复合材料进行过滤、洗涤后，在60℃下真空干燥3h。First, a certain amount of nano-Fe 2 O 3 (30 nm) was dispersed in 200 mL of ethyl acetate under the action of ultrasonic waves (ultrasonic power 1000 w,
实施例2，纳米CuO/AP催化复合材料的制备Embodiment 2, the preparation of nanometer CuO/AP catalytic composite material
首先在超声波作用下(超声功率为1200w，超声频率为107Hz，超声时间为20min)，将一定量的纳米CuO分散在300mL乙酸乙酯中。然后在0.4MPa氮气的作用下，将10mL的AP饱和DMF溶液压入结晶罐中，则AP将会以纳米CuO为核，在其表面生长最后形成纳米CuO/AP复合粒子。将制得的纳米复合材料进行过滤、洗涤后，在60℃下真空干燥3h。First, a certain amount of nano-CuO was dispersed in 300 mL of ethyl acetate under the action of ultrasonic waves (ultrasonic power 1200 w,
实施例3，与实施例1基本相同，但有以下改变：Embodiment 3 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为Co2O3；所述的纳米催化剂粒径大小为10nm。The nano-catalyst is Co 2 O 3 ; the particle size of the nano-catalyst is 10nm.
所述的高氯酸铵的溶剂选水；所述的高氯酸铵的非溶剂选乙醇。The solvent of the ammonium perchlorate is water; the non-solvent of the ammonium perchlorate is ethanol.
实施例4，与实施例1基本相同，但有以下改变：Embodiment 4 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为纳米金属粉Ni；所述的纳米催化剂粒径大小为10nm。The nano-catalyst is nano-metal powder Ni; the particle size of the nano-catalyst is 10nm.
所述的高氯酸铵的溶剂选择丙酮；所述的高氯酸铵的非溶剂选择乙酸乙酯。The solvent of the ammonium perchlorate is selected from acetone; the non-solvent of the ammonium perchlorate is selected from ethyl acetate.
实施例5，与实施例1基本相同，但有以下改变：Embodiment 5 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为纳米金属粉Cu；所述的纳米催化剂粒径大小为5nm。The nano-catalyst is Cu nano-metal powder; the particle size of the nano-catalyst is 5nm.
所述的高氯酸铵的溶剂为DMF；所述的高氯酸铵的非溶剂选择乙酸乙酯。The solvent of the ammonium perchlorate is DMF; the non-solvent of the ammonium perchlorate is ethyl acetate.
实施例6，与实施例1基本相同，但有以下改变：Embodiment 6 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为Al的纳米金属粉；所述的纳米催化剂粒径大小为100nm。The nano-catalyst is Al nano-metal powder; the particle size of the nano-catalyst is 100nm.
实施例7，与实施例1基本相同，但有以下改变：Embodiment 7 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为Fe2O3、CuO和Co2O3的复合纳米氧化物粉。The nano catalyst is composite nano oxide powder of Fe 2 O 3 , CuO and Co 2 O 3 .
实施例8，与实施例1基本相同，但有以下改变：Embodiment 8 is basically the same as Embodiment 1, but has the following changes:
所述的纳米催化剂为Ni、Cu和Al的复合纳米金属粉。The nano catalyst is composite nano metal powder of Ni, Cu and Al.
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| 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 |
| CN115925500B (en) * | 2022-05-25 | 2024-08-06 | 南京理工大学 | A solid propellant and a method for preparing the same |
| CN115947640B (en) * | 2023-01-31 | 2024-05-17 | 南京师范大学 | Aluminum powder/fluoropolymer/ammonium perchlorate energetic composite particles 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 | A method for preparing zirconium hydride-coated ammonium perchlorate composite energetic materials through solvent anti-solvent |
| CN117285008B (en) * | 2023-09-08 | 2024-11-05 | 淮阴师范学院 | Preparation method of butterfly-shaped micron ammonium perchlorate |
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