CN108217604B - Preparation method of hybrid powder material - Google Patents
Preparation method of hybrid powder material Download PDFInfo
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- CN108217604B CN108217604B CN201810095922.3A CN201810095922A CN108217604B CN 108217604 B CN108217604 B CN 108217604B CN 201810095922 A CN201810095922 A CN 201810095922A CN 108217604 B CN108217604 B CN 108217604B
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Abstract
The invention discloses a preparation method of a hybrid powder material by a gas phase method, which comprises the steps of igniting first mixed gas, spraying second mixed gas in a mode of surrounding flame formed by combustion of the first mixed gas, igniting the second mixed gas, enabling the flame formed by combustion of the second mixed gas and the flame formed by combustion of the first mixed gas to be converged and then enter a reaction container together. The preparation method of the hybrid powder material adopts a gas phase method to prepare the hybrid powder material, the second mixed gas is sprayed out in a mode of surrounding the flame formed by the combustion of the first mixed gas, the flame formed by the combustion of the second mixed gas can be intersected with the flame formed by the combustion of the first mixed gas and can jointly enter a reaction container, so that a coated powder material formed by coating the oxide generated by the second raw material on the oxide generated by the first raw material can be formed, and a hybrid powder material of a grid structure formed by interpenetrating the oxide generated by the second raw material and the oxide generated by the first raw material can also be formed.
Description
Technical Field
The invention relates to the field of powder materials, in particular to a preparation method of a hybrid powder material.
Background
The gas phase process is one of the main technological processes for preparing high purity superfine powder material. The products produced by the present method include fumed silica, fumed alumina, fumed titanium oxide, etc. the main process is to vaporize precursors of oxide powder materials (such as silicon tetrachloride, aluminum chloride, titanium tetrachloride, etc.) and then perform high-temperature hydrolytic condensation to obtain oxide powder, and the reaction principle is as follows:
MClx+H2+O2→M2Ox+HCl
wherein M is Si, Al, Ti, Zr, etc., and X is a natural number corresponding to the valence of the corresponding metal element.
The basic process flow of the gas phase method powder material production is similar (such as the process flows disclosed in patents of US3954945, US4048290, ZL02149782.6 and the like), and basically comprises the following process flows: (1) raw material vaporization: vaporizing the precursor; (2) mixing raw materials: mixing the precursor with hydrogen and oxygen (air); (3) reaction: carrying out high-temperature hydrolysis reaction on the precursor; (4) particle aggregation: oxide particles produced by the reaction are aggregated, so that the collection is convenient; (5) gas-solid separation: separating the oxide particles from the reaction by-product gas and the excess gas; (6) deacidifying: removing the by-products in the reaction process and the by-products adsorbed on the surface of the oxide powder.
However, the existing gas phase method processes are all used for preparing simple oxide powder materials, and basically do not have composite (hybrid) preparation technologies for various oxide powders. Moreover, the prior art is adopted to prepare the oxide hybrid material by the vapor phase method, and due to the problem of equipment structure design, the structure of the hybrid material is difficult to control, the product stability also has a great problem, and industrialization is difficult to realize. At present, the products are developed by adopting a sol-gel method, but the sol-gel method is very difficult to control the products, and is difficult to obtain uniform and stable metal oxide hybrid materials, and the structure and the performance of the metal oxide hybrid materials prepared by adopting the sol-gel method are greatly different from those of the products obtained by a gas phase method process.
Disclosure of Invention
Based on this, there is a need for a method for preparing hybrid powder materials by a gas phase method.
A preparation method of a hybrid powder material comprises the following steps:
the first raw material and the second raw material are subjected to vaporization treatment to respectively obtain a first vaporized raw material and a second vaporized raw material;
uniformly mixing the first vaporized raw material with the reaction gas to obtain a first mixed gas, and uniformly mixing the second vaporized raw material with the reaction gas to obtain a second mixed gas;
igniting the first mixed gas, spraying the second mixed gas in a mode of surrounding flame formed by the combustion of the first mixed gas, and igniting the second mixed gas, so that the flame formed by the combustion of the second mixed gas and the flame formed by the combustion of the first mixed gas are converged and then enter a reaction container together;
and collecting a reaction product generated in the reaction container to obtain the catalyst.
In one embodiment, the method for preparing a hybrid powder material further comprises the step of adjusting the spraying position of the first mixed gas relative to the spraying position of the second mixed gas to prepare hybrid powder materials with different structures.
In one embodiment, the second mixed gas is ejected in an inclined direction toward the reaction container.
In one embodiment, the method for preparing the hybrid powder material further comprises the steps of preparing a third mixed gas, and enabling a flame formed by burning the third mixed gas to cover a flame formed by burning the first mixed gas.
In one embodiment, the third mixed gas comprises the first vaporized material and O2。
In one embodiment, the first and second materials are selected from SiCl4、CH3SiCl3、TiCl4、AlCl3Or ZrCl4(ii) a The reaction gas contains oxygen and a combustible gas capable of reacting with the oxygen to produce moisture.
In one embodiment, the reactive gas is a mixture of oxygen and a combustible gas capable of reacting with oxygen to generate moisture, or a mixture of air and a combustible gas capable of reacting with oxygen to generate moisture, and the combustible gas is selected from H2、CH4、C2H6Or CH3OCH3. In one embodiment, H in the first mixed gas and the second mixed gas2And O2Are in excess.
In one embodiment, the hybrid powder material preparation method uses a powder material preparation device for reaction preparation, wherein the powder material preparation device comprises a vaporizer, a mixed gas supply mechanism, a gas mixing mechanism, a cross gas supply mechanism and a reaction chamber; the vaporizer is used for vaporizing raw materials, the vaporizer has a plurality of, wherein have one at least the vaporizer with mix gas supply mechanism intercommunication in order to mix the gas supply mechanism and provide first gasification raw materials, and wherein have one at least the vaporizer with mix gas mechanism intercommunication in order to mix the gas mechanism and provide the second gasification raw materials, mix gas supply mechanism be used for with first gasification raw materials and reaction gas misce bene, mix gas supply mechanism has mixed gas outlet, mix gas mechanism be used for with second gasification raw materials and reaction gas misce bene, mix gas mechanism with cross gas supply mechanism intercommunication, cross gas supply mechanism has annular cross gas outlet, cross gas outlet is located mix the gas outlet with between the entry of reaction chamber, just cross the gas outlet with the distance between the mixed gas outlet is adjustable, the flame ignited at the cross gas outlet can be converged with the flame ignited at the mixed gas outlet and then jointly enters the reaction chamber.
In one embodiment, the mixed gas supply mechanism comprises a main body part and a jacket part, the main body part is in a hollow tubular shape, the main body part is provided with a gas mixing chamber and a plurality of gas inlets communicated with the gas mixing chamber, the jacket part is sleeved on the main body part and has a gap with the main body part, the jacket part is provided with a gas inlet communicated with the gap, and the main body part and the jacket part are opened at one end to form the mixed gas outlet;
and a plurality of layers of gas dispersion plates are arranged in the gas mixing cavity, and the gas flow channel in the gas mixing cavity is divided into a plurality of strands by each layer of gas dispersion plate.
In one embodiment, the cross air supply mechanism is a hollow cylindrical structure, the inner side of the cross air supply mechanism is provided with a circular cross air outlet, the opening direction of the cross air outlet is inclined towards the reaction chamber, the outer side of the cross air outlet is provided with an air inlet communicated with the cross air outlet, and the shell of the cross air supply mechanism is provided with a buffer cavity communicated with the cross air outlet and the air inlet.
The preparation method of the hybrid powder material adopts a gas phase method to prepare the hybrid powder material, the second mixed gas is sprayed out in a mode of surrounding the flame formed by the combustion of the first mixed gas, the flame formed by the combustion of the second mixed gas can be intersected with the flame formed by the combustion of the first mixed gas and can jointly enter the reaction container, so that a coated powder material formed by coating the oxide generated by the second raw material on the oxide generated by the first raw material can be formed, and a hybrid powder material of a grid structure formed by interpenetrating the oxide generated by the second raw material and the oxide generated by the first raw material can also be formed.
Drawings
Fig. 1 is a schematic structural diagram of a powder material preparation apparatus according to an embodiment;
FIG. 2 is a schematic view of the vaporizer of FIG. 1;
FIG. 3 is a schematic structural view of the mixing gas supply mechanism in FIG. 1;
FIG. 4 is a schematic structural view of the cross air supply mechanism of FIG. 1;
FIG. 5 is a schematic view showing the combination of the mixing gas supply mechanism, the cross gas supply mechanism and the reaction chamber;
FIG. 6 is a schematic flow chart of a hybrid powder material preparation method according to an embodiment;
FIG. 7 is an infrared spectrum.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The principle of preparing the oxide powder material by the gas phase method process is as follows:
it has been found that in the preparation of a hybrid material of two or more oxides, the key controlling factor is to ensure the precursors of the different oxides (MCl)x) Stable supply of (2). Because the whole production process of the gas phase method process is continuous and dynamic, if the stability of different element ratios of the hybrid material is ensured, the ratio of various precursors entering a reaction system is ensured to be stable. In addition, it is necessary to ensure uniform reaction of various raw materials, so as to realize control of the structure of the hybrid material.
The invention provides a powder material preparation device for preparing a metal oxide hybrid material by adopting a vapor phase method process. In addition, by controlling the sequence of the various precursor gases entering the reaction chamber, oxide hybrid materials with different structures can be obtained.
Specifically, as shown in fig. 1, the powder material preparation apparatus 10 according to an embodiment of the present invention includes a vaporizer 100, a mixing gas supply mechanism 200, a gas mixing mechanism 300, a cross gas supply mechanism 400, and a reaction chamber 500. The vaporizer 100 is used to vaporize a raw material. In the present embodiment, there are a plurality of vaporizers 100, at least one of the vaporizers 100 is communicated with the mixing gas supply mechanism 200 to supply the first vaporized material to the mixing gas supply mechanism 200, and at least one of the vaporizers 100 is communicated with the gas mixing mechanism 300 to supply the second vaporized material to the gas mixing mechanism 300. The mixing gas supply mechanism 200 is used for uniformly mixing the first vaporized raw material with the reaction gas. The gas mixing mechanism 300 is used for uniformly mixing the second vaporized raw material with the reaction gas. The reaction gas is mixed gas of hydrogen and oxygen according to a certain proportion.
As shown in fig. 3, 4 and 5, in the present embodiment, the mixing air supply mechanism 200 has a mixing air outlet 201. The air mixing mechanism 300 communicates with a cross air supply mechanism 400, and the cross air supply mechanism 400 has an annular cross air outlet 402. The cross air outlet 402 is located between the mixed air outlet 201 and the inlet of the reaction chamber 500, the distance between the cross air outlet 402 and the mixed air outlet 201 is adjustable, and the flame 21 ignited at the cross air outlet 402 can be converged with the flame 22 ignited at the mixed air outlet 201 and then enter the reaction chamber 500 together. The flame 21 and the flame 22 are intersected and then enter the reaction chamber 500 together to perform a hybrid reaction of the powder material, so as to obtain the hybrid material, for example, a mixed gas of a first vaporized raw material and a reaction gas can be ignited through the mixed gas outlet 201, a mixed gas of a second vaporized raw material and the reaction gas can be ignited through the cross gas outlet 402, and by adjusting the distance between the cross gas outlet 402 and the mixed gas outlet 201, a coated hybrid powder material in which powder particles obtained by the reaction of the first vaporized raw material are coated by powder particles obtained by the reaction of the second vaporized raw material, or a hybrid powder material in which two kinds of particles are in an interpenetrating grid structure can be obtained. The powder material preparation device 10 is exquisite in structural design, can be used for producing hybrid powder materials by a gas phase method, and has the advantages of wide application range and strong applicability.
Referring to fig. 2, in the present embodiment, the vaporizer 100 includes a feeding mechanism 110, a heating mechanism 120, a heat exchanging mechanism 130, a discharging mechanism 140, and a control mechanism (not shown). The heat exchanging mechanism 130 has a vaporization chamber 131 and a heating chamber 132. The vaporization chamber 131 is provided with a pressure detection element (P in the drawing). The feeding mechanism 110 and the discharging mechanism 140 are respectively communicated with the vaporizing chamber 131. The heating mechanism 120 is in communication with the heating chamber 132. The feeding mechanism 110, the discharging mechanism 140 and the heating mechanism 120 are provided with temperature detecting elements (T in the figure). The control mechanism is used for controlling the feeding mechanism 110, the discharging mechanism 140 and the heating mechanism 120.
Further, the feeding mechanism 110 of the present embodiment includes a feeding pipe 111, and a feeding flowmeter 112 and a feeding control valve 113 provided on the feeding pipe 111, wherein a temperature detection element is provided on the feeding pipe 111; the heating mechanism 120 comprises a circulating pipe 121 and a temperature control valve 122 arranged on the circulating pipe 121, a temperature detection element is arranged at one end of the circulating pipe 121 connected with the heating cavity 132, and the circulating pipe 121 is communicated with the heating cavity 132 in a mode of liquid inlet from the bottom and liquid outlet from the top so as to perform sufficient heat exchange between the heating cavity 132 and the substances in the vaporizer 131; the heat exchange mechanism 130 is a heat exchange kettle with a heating cavity 132 covering the vaporization cavity 131; the discharging mechanism 140 comprises a discharging pipe 141 and a discharging flowmeter 142 arranged on the discharging pipe 141, and a temperature detecting element is arranged on the discharging pipe; the control mechanism is connected with the feed flow meter 112, the feed control valve 113, the temperature control valve 122 and the discharge flow meter 142 to form a comprehensive control system, so as to control the opening degree of the corresponding valve through relevant signals (such as temperature, pressure and flow signals) collected in time.
The vaporizer 100 having the above-described structure can achieve uniform and stable vaporization and supply of raw materials, and ensure stability of subsequent hybridization reactions.
Referring to fig. 3 again, in the present embodiment, the mixing and gas-supplying mechanism 200 includes a main body portion 210 and a jacket portion 220. The main body portion 210 has a gas mixing chamber 211 and gas inlets 212 and 213 communicating with the gas mixing chamber 211 for entry of vaporized raw materials and reaction gases, the vaporized raw materials may enter via the gas inlet 212, and the reaction gases may enter via the gas inlet 213; or a part of the reaction gas is introduced together with the vaporized raw material through the gas inlet 212 and the rest of the reaction gas is introduced through the gas inlet 213. The jacket portion 220 is disposed on the main body portion 210 and has a gap 221 with the main body portion 210. The jacket portion 220 has an inlet port 222 for entry of the vaporized raw material and/or the reaction gas, which communicates with the gap 221. The main body 210 and the jacket 220 are open at one end to form a mixing gas outlet 201. The mixing gas supply mechanism 200 of the present embodiment includes a main body 210 and a jacket 220, and the gas ejected from the gas mixing chamber 211 of the main body 210 is combusted to form a flame 223, and the gas ejected from the gap 221 is combusted to form a flame 224, and the flame 224 is wrapped around the flame 223 to serve as a protection flame.
The main body 210 of the present embodiment has a hollow tubular shape, and a multi-layer gas distribution plate 230 is provided in the gas mixing chamber 211. The gas distribution plate 230 may be porous or divergent. The gas distribution plate 230 of each layer divides the gas flow path in the gas mixing chamber 211 into a plurality of strands. Through setting up gas dispersion board 230, can be so that first gasification raw materials and reactant gas intensive mixing even, especially with gas dispersion board 230 layering setting, can further improve first gasification raw materials and reactant gas's mixed effect.
Further, the inside diameter of main body 210 of the present embodiment gradually decreases from the end where air inlets 212 and 213 are provided to the end where air-fuel mixture outlet 201 is provided. In the illustrated embodiment, the tapering is distributed tapering, such as may be formed in multiple sections, each section having a substantially uniform inner diameter, with the inner diameter of the latter section decreasing from the end where inlets 212 and 213 are located to the end where mixing outlet 201 is located. By gradually reducing the inner diameter of the gas mixing chamber 211, the mixing effect of the first vaporized raw material and the reaction gas can be further improved, and the pressure of the mixed gas at the mixed gas outlet 210 can be increased, facilitating the ejection of the flame 223. Further, the gap between the jacket part 220 and the main body part 210 is also gradually reduced at the end near the mixing gas outlet 201, which also increases the pressure of the gas jet at the mixing gas outlet 210, facilitating the flame 224 to be jetted.
In the present embodiment, the temperature detection element 240 is provided in the mixed air supply mechanism 200. The temperature detecting element 240 can detect the temperature of the gas in the gas mixing chamber 211 in real time, so as to facilitate real-time mastering of the temperature condition in the gas mixing chamber 211 and ensure that the first raw material is always in a vaporization state.
Referring to fig. 4, the cross air supply mechanism 400 of the present embodiment has a hollow cylindrical structure. The cross air supply mechanism 400 has a circular cross air outlet 402 on the inside and an air inlet 401 on the outside communicating with the cross air outlet 402. The housing of the cross air supply mechanism 400 is provided with a buffer chamber 403 communicating the cross air outlet 402 and the air inlet 401.
Further, in the present embodiment, there are two air inlets 401 of the cross air supply mechanism 400, and the two air inlets 401 are disposed opposite to each other; the cross air outlet 402 is disposed near one end of the cross air supply mechanism 400, and the other end of the cross air supply mechanism 400 is fixedly connected to one end of the inlet of the reaction chamber 500, for example, by a flange structure. The opening direction of the cross gas outlet 402 is inclined toward the reaction chamber 500 so that the mixed gas of the second vaporized raw material and the reaction gas is inclined at a predetermined angle into the reaction chamber 500.
The powder material preparation apparatus 10 includes a vaporizer 100, a mixing gas supply mechanism 200, a gas mixing mechanism 300, a cross gas supply mechanism 400, and a reaction chamber 500. As shown in fig. 5, the mixed gas supply mechanism 200 has a mixed gas outlet 201, the cross gas supply mechanism 400 has an annular cross gas outlet 402, the cross gas outlet 402 is located between the mixed gas outlet 201 and the inlet of the reaction chamber 500, and the distance between the cross gas outlet 402 and the mixed gas outlet 201 is adjustable, so that the flame ignited at the cross gas outlet 402 can be intersected with the flame ignited at the mixed gas outlet 201 and then enter the reaction chamber 500 together to perform the hybridization reaction of the powder material, thereby obtaining the hybrid material.
The embodiment also provides a preparation method of the hybrid powder material, as shown in fig. 6, the preparation method comprises the following steps:
step S1: the first raw material and the second raw material are subjected to vaporization treatment to respectively obtain a first vaporized raw material and a second vaporized raw material;
step S2: uniformly mixing the first vaporized raw material with the reaction gas to obtain a first mixed gas, and uniformly mixing the second vaporized raw material with the reaction gas to obtain a second mixed gas;
step S3: igniting the first mixed gas, spraying the second mixed gas in a mode of surrounding flame formed by the combustion of the first mixed gas, and igniting the second mixed gas, so that the flame formed by the combustion of the second mixed gas and the flame formed by the combustion of the first mixed gas are converged and then jointly enter a reaction container;
step S4: and collecting a reaction product generated in the reaction container to obtain the catalyst.
In this embodiment, the method for producing a hybrid powder material further includes a step of adjusting the ejection position of the first mixed gas with respect to the ejection position of the second mixed gas to produce a hybrid powder material having a different structure, and for example, the ejection position of the second mixed gas may be adjusted to be close to the ejection position of the first mixed gas to form a hybrid powder material having an interpenetrating network structure, or the ejection position of the second mixed gas may be adjusted to have a certain distance, for example, 30cm, from the ejection position of the first mixed gas to form an encapsulated powder material in which an oxide produced from the second raw material coats an oxide produced from the first raw material.
Preferably, the ejection direction of the second mixed gas is inclined toward the reaction container.
Further, the preparation method of the hybrid powder material also comprises the steps of preparing a third mixed gas, and enabling flame formed by combustion of the third mixed gas to coat flame formed by combustion of the first mixed gas. The third mixed gas contains the first vaporized raw material and O2。
The first and second materials are selected from SiCl4、CH3SiCl3、TiCl4、AlCl3Or ZrCl4(ii) a The reaction gas contains oxygen and a combustible gas capable of reacting with the oxygen to produce moisture. Specifically, the reaction gas is a mixed gas of oxygen and a combustible gas capable of reacting with oxygen to generate moisture, or a mixed gas of air and a combustible gas capable of reacting with oxygen to generate moisture, and the combustible gas is selected from H2、CH4、C2H6Or CH3OCH3. Combustible gas and O in the first mixed gas and the second mixed gas2Are in excess.
The preparation method of the hybrid powder material can directly use the powder material preparation device 10 for production and preparation, and has the advantages of simple process steps, high production efficiency and the like. The preparation method of the hybrid powder material adopts a gas phase method to prepare the hybrid powder material, the second mixed gas is sprayed out in a mode of surrounding the flame formed by the combustion of the first mixed gas, the flame formed by the combustion of the second mixed gas can be intersected with the flame formed by the combustion of the first mixed gas and can jointly enter a reaction container, so that a coated powder material formed by coating the oxide generated by the second raw material on the oxide generated by the first raw material can be formed, and a hybrid powder material of a grid structure formed by interpenetrating the oxide generated by the second raw material and the oxide generated by the first raw material can also be formed.
The apparatus and method for producing a powdery material of the present invention will be described in further detail with reference to specific examples.
Introduction to the principle
Preparation of SiO2/Al2O3、SiO2/TiO2Or Al2O3/TiO2Hybrid materials
In which SiO is prepared2SiCl is selected as the precursor (raw material)4，Al2O3AlCl is selected as the precursor3Preparation of TiO2The precursor is SiCl4Their respective reaction principles are as follows:
as can be seen from the reaction formulas (1) to (3), the raw material ratios in the reaction formulas are different, and SiCl is present at room temperature4Is liquid, its boiling point is 57.6 ℃; and AlCl3Is solid (powder) at normal temperature and begins to sublimate at 178 ℃; TiCl (titanium dioxide)4Is liquid at normal temperature and has a boiling point of 136.4 ℃.
Because the states of various precursors are different and the vaporization temperatures are greatly different, the SiO is prepared2/Al2O3When the material is hybridized, different raw material vaporizers are needed to be used respectively, and the raw material vaporization rate of the vaporizers needs to be strictly controlled, so that the stable proportion of the two precursor gases can be ensured. Alternatively, if a conventional vapor phase oxidation process is used, two precursor gases are mixed with H2And O2Mixing, then carrying out a combustion reaction,due to the reaction gas (H) required for the respective reaction of the two precursors2And O2) In contrast, local reaction gas shortage or excess is easily caused, and finally the surface structure of the hybrid material is unstable. Moreover, the hybrid material obtained by the method is only SiO2And Al2O3Disordered hybridization.
In the preparation of SiO2/TiO2In the case of hybrid materials, although the precursors of the two are both liquid, the theoretical reaction gases required for the reaction are also the same, but the molar ratio is the same, and the mass ratio is greatly different because the molecular weights of the two are greatly different. In addition, because the difference between the vaporization temperatures of the two raw materials is close to 80 ℃, if the same raw material vaporizer is adopted to directly vaporize the mixed liquid raw materials, the uniform mixed gas of the two raw materials cannot be ensured due to the different vaporization rates of the two raw materials.
The powder material manufacturing apparatus 10 according to the present invention can solve the above problems, and can stably supply the raw material by using two vaporizers 100 to vaporize the raw material, respectively, and by linking signals such as temperature, pressure, and flow rate. To prepare SiO2/Al2O3Hybrid materials, SiCl4The vaporized reaction gas can enter from the gas inlet 212, the reaction gas enters from the gas inlet 213, and the reaction gas can be uniformly mixed after being acted by the gas dispersion plate 230 in the gas mixing chamber 211; AlCl3After vaporization, the gas is mixed with the reaction gas in the gas mixing mechanism 300 and then enters the cross gas supply mechanism 400 through the gas inlet 401. In addition, in the gas inlet 222, H may be introduced2，O2Or the mixed gas of the two is used as the protective gas of the inner flame. SiCl can be achieved by spacing the mixing gas supply mechanism 200 and the cross gas supply mechanism 400 by a distance4First burning to form SiO2Particles and then with AlCl3The flames converge so that Al2O3The particles may be in SiO2Growth of the surface of the particles to realize Al2O3Coated SiO2SiO of structure2/Al2O3A hybrid material. In addition, SiCl is added4And AlCl3Gas (es)The feeding positions of the two parts are exchanged, so that SiO can be realized2Coated with Al2O3SiO of structure2/Al2O3A hybrid material. If the upper mixed gas supply means 200 and the lower cross gas supply means 400 are connected together, SiO can be realized2And Al2O3SiO with particle interpenetrating network structure2/Al2O3And (3) preparing the hybrid material.
Example 1
Controlling SiCl in a first vaporizer4Has a vaporization rate of 6.0kg/h, vaporized SiCl4The temperature was controlled to 130 + -5 deg.C before entering the air inlet of the mixing air supply mechanism. The amount of hydrogen and oxygen is based on SiCl4：H2：O2Hydrogen was first mixed with SiCl in a 1:2.55:1.5 ratio (molar ratio)4The gas is mixed, enters the mixed gas supply mechanism from one gas inlet of the main body part, and is controlled to be at 150 +/-5 ℃ before entering the mixed gas supply mechanism. Oxygen (calculated by the oxygen content of 21 percent in the air) enters the mixed air supply mechanism from the other air inlet of the main body part, and the temperature is controlled to be 150 +/-5 ℃. In addition to SiCl4：O2Oxygen (calculated as the 21% oxygen content in air) at a ratio of 1:0.8 was fed from the inlet of the jacket into the gap between the jacket and the body, and the temperature was controlled at 150 ± 5 ℃.
AlCl3The raw material is vaporized in a second vaporizer, the vaporization rate is controlled to be 1.3kg/h, and the vaporized AlCl3Gas and H2And O2According to AlCl3：H2：O2After mixing, the mixed gas enters the cross gas supply mechanism from the gas inlet of the cross gas supply mechanism according to the proportion (molar ratio) of 1:1.65:1.05, and the temperature of the mixed gas before entering is kept to be 220 +/-5 ℃.
The distance between the mixed gas supply mechanism at the upper end and the cross gas supply mechanism at the lower end is kept at 30cm, and Al is prepared by the process2O3Coated SiO2SiO of structure2/Al2O3Hybrid material, denoted as sample # 1.
Example 2
The raw materials were supplied according to the process and ratio of example 1, and the process was repeatedThe end mixed gas supply mechanism is connected with the lower cross gas supply mechanism, the distance between the end mixed gas supply mechanism and the lower cross gas supply mechanism is 0cm, and SiO is prepared by the process2With Al2O3Interpenetrating network structure of SiO2/Al2O3Hybrid material, denoted as sample # 2.
Example 3
The raw materials are exchanged as in example 1, and AlCl is controlled in a first vaporizer3Has a vaporization rate of 2.0kg/h and vaporized AlCl3The temperature is controlled to be 220 +/-5 ℃ before entering the air inlet of the mixed air supply mechanism. The amount of hydrogen and oxygen is determined by AlCl3：H2：O2Hydrogen was first mixed with AlCl in a 1:2.05:1.25 ratio (molar ratio)3The gas is mixed, enters the mixed gas supply mechanism from one gas inlet of the main body part, and is controlled to be at 220 +/-5 ℃ before entering the mixed gas supply mechanism. Oxygen (calculated by the oxygen content of 21 percent in the air) enters the mixed air supply mechanism from the other air inlet of the main body part, and the temperature is controlled to be 220 +/-5 ℃. In addition, according to AlCl3：O2Oxygen (calculated as the 21% oxygen content in air) at a ratio of 1:0.85 enters the gap between the jacket portion and the main body portion from the air inlet of the jacket portion, and the temperature is controlled at 220 ± 5 ℃.
SiCl4The feedstock was vaporized from the second vaporizer at a controlled vaporization rate of 3kg/h and the vaporized SiCl4Gas and H2And O2According to SiCl4：H2：O2After mixing according to the proportion (molar ratio) of 1:2.45:1.45, the mixed gas enters the cross gas supply mechanism from the gas inlet of the cross gas supply mechanism, and the temperature of the mixed gas before entering is kept to be 150 +/-5 ℃.
The distance between the mixed gas supply mechanism at the upper end and the cross gas supply mechanism at the lower end is kept at 30cm, and the SiO is prepared by the process2Coated with Al2O3SiO of structure2/Al2O3Hybrid material, denoted as sample # 3.
By the similar process, the TiO can be respectively prepared by changing the types and the combinations of the raw materials2/SiO2，TiO2/Al2O3，TiO2/ZrO2，SiO2/ZrO2，Al2O3/ZrO2And the like.
The above samples were tested for SiO by dissolution with HF2The test results are shown in table 1. In addition, infrared spectroscopy was also performed on each sample, and the results are shown in FIG. 7.
TABLE 1
| Sample name | Theoretical SiO2Content (wt.) | |
| 1# | 68.17％ | 45.17％ |
| 2# | 68.17％ | 57.66％ |
| 3# | 40.93％ | 38.85％ |
From the test results in Table 1, the sample No. 1 is Al2O3Coated SiO2SiO of structure2/Al2O3The theoretical silica content of the hybrid material is 68.17%, but the actual measurement result is 45.17%, which is greatly deviated from the theoretical value mainly because there is a part of SiO2Is covered with Al2O3Completely coated, HF hardly dissolves the coated SiO2Therefore, the measured content is lower than the theoretical content. However, since silica is predominant, a large portion of silica is only partially coated and therefore is still dissolved by HF. The 2# sample is designed to be SiO2With Al2O3Interpenetrating network structure of SiO2/Al2O3Hybrid materials, since there is also part of SiO2Is covered with Al2O3And coating, so the measured content of the silicon dioxide is slightly lower than the theoretical content, which is relatively consistent with the result of the interpenetrating network structure. Sample # 3 is SiO2Coated with Al2O3SiO of structure2/Al2O3The actual measurement result of the content of silicon dioxide is close to the theoretical content of the hybrid material, SiO2Almost entirely outside.
From spectrum 7 of the IR spectrum, although part of the characteristic peaks are masked due to the superposition effect, the spectrum of sample No. 1 is compared with that of pure SiO2And pure Al2O3The spectrogram can see that in the 1# sample spectrogram, the peak intensity is 570cm-1And 670cm-1The characteristic peak of alumina is obviously existed nearby, which indicates that the surface of the sample No. 1 is alumina; comparing the 3# sample spectrogram with pure SiO2And pure Al2O3The spectrum can be seen. Basically all the characteristic peaks of silicon dioxide and aluminum oxide are basically covered, which indicates that the No. 3 sample is basically SiO2Coated with Al2O3The structure of (1).
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A preparation method of a hybrid powder material is characterized by comprising the following steps:
carrying out vaporization treatment on a first raw material and a second raw material to respectively obtain a first vaporized raw material and a second vaporized raw material, wherein the first raw material and the second raw material are selected from SiCl4、CH3SiCl3、TiCl4、AlCl3Or ZrCl4；
Uniformly mixing a first gasification raw material and a reaction gas to obtain a first mixed gas, uniformly mixing a second gasification raw material and the reaction gas to obtain a second mixed gas, wherein the reaction gas contains oxygen and a combustible gas capable of reacting with the oxygen to generate moisture, and H in the first mixed gas and the second mixed gas2And O2Are all excessive;
igniting the first mixed gas, spraying the second mixed gas in a mode of surrounding flame formed by the combustion of the first mixed gas, and igniting the second mixed gas, so that the flame formed by the combustion of the second mixed gas and the flame formed by the combustion of the first mixed gas are converged and then enter a reaction container together;
collecting a reaction product generated in the reaction container to obtain the catalyst;
the preparation method of the hybrid powder material uses a powder material preparation device for reaction preparation, wherein the powder material preparation device comprises a vaporizer, a mixed gas supply mechanism, a gas mixing mechanism, a cross gas supply mechanism and a reaction chamber; the vaporizer is used for vaporizing raw materials, the vaporizer has a plurality of, wherein have one at least the vaporizer with mix gas supply mechanism intercommunication in order to mix the gas supply mechanism and provide first gasification raw materials, and wherein have one at least the vaporizer with mix gas mechanism intercommunication in order to mix the gas mechanism and provide the second gasification raw materials, mix gas supply mechanism be used for with first gasification raw materials and reaction gas misce bene, mix gas supply mechanism has mixed gas outlet, mix gas mechanism be used for with second gasification raw materials and reaction gas misce bene, mix gas mechanism with cross gas supply mechanism intercommunication, cross gas supply mechanism has annular cross gas outlet, cross gas outlet is located mix the gas outlet with between the entry of reaction chamber, just cross the gas outlet with the distance between the mixed gas outlet is adjustable, the flame ignited at the cross gas outlet can be converged with the flame ignited at the mixed gas outlet and then jointly enters the reaction chamber;
the vaporizer includes feed mechanism, heating mechanism, heat transfer mechanism, discharge mechanism and control mechanism, heat transfer mechanism has vaporization chamber and heating chamber, the vaporization chamber is equipped with pressure detection element, feed mechanism reaches discharge mechanism respectively with vaporization chamber intercommunication, heating mechanism with the heating chamber intercommunication, feed mechanism discharge mechanism and heating mechanism are equipped with temperature detection element, control mechanism is used for control feed mechanism discharge mechanism reaches heating mechanism.
2. The method of preparing a hybrid powder material according to claim 1, further comprising the step of adjusting the ejection position of the first mixed gas with respect to the ejection position of the second mixed gas to prepare a hybrid powder material having a different structure.
3. The method for preparing a hybrid powder material according to claim 1, wherein the spraying direction of the second mixed gas is inclined toward the reaction vessel.
4. The method of preparing a hybrid powder material according to claim 1, further comprising the step of preparing a third mixed gas and coating the flame formed by the combustion of the first mixed gas with the flame formed by the combustion of the third mixed gas.
5. The method of preparing hybrid powder material according to claim 4, wherein the third mixed gas comprises the first vaporized raw material andO2。
6. the method for preparing a hybrid powder material according to claim 1, wherein the gas mixing and supplying mechanism comprises a main body part and a jacket part, the main body part is in a hollow tubular shape, the main body part comprises a gas mixing chamber and a plurality of gas inlets communicated with the gas mixing chamber, the jacket part is sleeved on the main body part and has a gap with the main body part, the jacket part comprises a gas inlet communicated with the gap, and the main body part and the jacket part are opened at one end to form the gas mixing outlet;
and a plurality of layers of gas dispersion plates are arranged in the gas mixing cavity, and the gas flow channel in the gas mixing cavity is divided into a plurality of strands by each layer of gas dispersion plate.
7. The method for preparing hybrid powder material according to claim 1, wherein the cross gas supply mechanism is a hollow cylindrical structure, the inner side of the cross gas supply mechanism is provided with a circular cross gas outlet, the opening direction of the cross gas outlet is inclined towards the reaction chamber, the outer side of the cross gas outlet is provided with a gas inlet communicated with the cross gas outlet, and the shell of the cross gas supply mechanism is provided with a buffer cavity communicated with the cross gas outlet and the gas inlet.
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Address after: 510000 room 508, laboratory building, No. 15, Nanxiang Third Road, Science City, Guangzhou high tech Industrial Development Zone, Guangdong Province Co-patentee after: Hubei HuiFu nano materials Co., Ltd Patentee after: Guangzhou Hui Fu Research Institute Co.,Ltd. Address before: 510663 508 laboratory building 15, Nanxiang three road, science and Technology City, Guangzhou high tech Industrial Development Zone, Guangdong, China Co-patentee before: YICHANG HUIFU SILICON MATERIAL Co.,Ltd. Patentee before: Guangzhou Hui Fu Research Institute Co.,Ltd. |