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CN112717848A - Pulse type spray evaporation flame synthesis method and device - Google Patents

Pulse type spray evaporation flame synthesis method and device Download PDF

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Publication number
CN112717848A
CN112717848A CN202011499440.8A CN202011499440A CN112717848A CN 112717848 A CN112717848 A CN 112717848A CN 202011499440 A CN202011499440 A CN 202011499440A CN 112717848 A CN112717848 A CN 112717848A
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China
Prior art keywords
flame
oxide
evaporation
precursor
spray
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Chinese (zh)
Inventor
田振玉
何忧
于丹
苏冠宇
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Institute of Engineering Thermophysics of CAS
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Institute of Engineering Thermophysics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D11/00—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
    • F23D11/10—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space the spraying being induced by a gaseous medium, e.g. water vapour
    • F23D11/22—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space the spraying being induced by a gaseous medium, e.g. water vapour the gaseous medium being vaporised fuel, e.g. for a soldering lamp, or other gaseous fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D11/00—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
    • F23D11/36—Details, e.g. burner cooling means, noise reduction means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D11/00—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
    • F23D11/36—Details, e.g. burner cooling means, noise reduction means
    • F23D11/44—Preheating devices; Vaporising devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00157—Controlling the temperature by means of a burner

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Abstract

A pulse type spray evaporation flame synthesis method and a device thereof, wherein the method comprises the following steps: injecting the precursor solution into the flame for reaction by pulse atomization, forming a prefabricated material core by the precursor in the precursor solution, and depositing to obtain the final product. The invention combines the pulse type spray evaporator with the flame spray pyrolysis method, and accurately adjusts the concentration of the precursor in the liquid raw material and the spraying frequency and the opening time of the spray nozzle, thereby controlling the thickness of the film, the stoichiometry of the catalyst and the growth rate; meanwhile, the performance reduction of the device caused by the concentration fluctuation of the precursor solution is avoided.

Description

Pulse type spray evaporation flame synthesis method and device
Technical Field
The invention relates to the field of chemical synthesis and combustion, in particular to a pulse type spray evaporation flame synthesis method and a device.
Background
Thin films and nanomaterials are used in a wide variety of modern technologies. Such as: the application of the ferromagnetic film in computer storage equipment, pharmaceuticals, thin film batteries, dye-sensitized solar cells and the like, and the use of the high-hardness ceramic film on cutters. Nanomaterials play a key role in many fields of engineering, including energy (nanoelectronics, nanocatalysis, fossil fuel combustion), environment (air pollution, climate change) and biotechnology (medical diagnostics, drug delivery), etc. With the increasing requirements of people on the performance and the advancement of thin film materials and nanoparticles, the efficient and controllable preparation of the thin film materials and the nanoparticles is more and more concerned, and the deposition methods of the thin films and the nanoparticles can be divided into two types, namely physical methods and chemical methods according to different preparation process principles. The former includes mechanical grinding, Physical Vapor Deposition (PVD), laser ablation, molecular beam epitaxy, thermal Deposition and sputtering. Due to physical methods, it is difficult to effectively control the particle size, and the material preparation efficiency is low, so that the method is generally only suitable for specific materials. The latter mainly includes vapor deposition methods and solution techniques. The Vapor Deposition method is classified into Chemical Vapor Deposition (CVD) and Atomic Layer Epitaxy (ALE). The solution technology comprises spray pyrolysis method, sol-gel method, dipping method, coprecipitation method, rotary dipping pulling method and other technologies which all need to use precursor solution. The methods of laser ablation, vapor deposition and sol-gel methods with high equivalent ratio all require the use of specialized equipment, such as vacuum units, high power lasers and expensive precursor materials. This results in extremely costly processes. The flame spray pyrolysis method has the advantages of simple process and easy control of the size of the final product. In particular, the precursor can be dissolved in the fuel in advance, the process of feeding the precursor into a thermal reaction zone (flame reactor) is simplified, and the aerosol can be rapidly quenched by flexibly using a high-speed atomizer.
There are several documents that have studied different flame pyrolysis processes. For example, in 2002, researchers have proposed a flame synthesis device that can regulate oxygenThe flow rate of the reagent to synthesize the nanomaterial. And the composition of the precursor/fuel to control the specific surface area of the catalyst. In 2005, another investigator optimized a flame spray pyrolysis apparatus for synthesizing perovskite mixed metal catalysts, primarily using CH in the igniter4/O2The flow rate of the mixture, as well as the flow rate and the linear velocity, optimize the feed rate of the precursor solution. In 2006, another work focused on a novel flame synthesis method that used gas and liquid precursors to produce nano-alumina catalysts. The method uses a high temperature flame to heat the feedstock and spray it into a condensing chamber where it is condensed into a nano-scale catalyst. In 2019, researchers have proposed an improvement to the flame synthesis apparatus for producing metal, non-oxidized ceramic and reduced metal oxide powders.
However, these methods are inefficient, and the main problems are that the diffusion of particles to the tube wall and thermophoresis processes exist in these methods, which results in a too wide size distribution of particles, which is not suitable for most cases, extremely poor versatility, and low yield. In addition, in the prior art, rotational flow flame and a technology of directly spraying the precursor solution into a reaction chamber after ultrasonically atomizing the precursor solution are generally used, the feeding frequency of a flame synthesis device and the duration of the atomized precursor solution are difficult to control, and thus concentration fluctuation of the precursor solution can be caused. Which in turn affects the particle size and properties, such as morphology, surface area, of the final product.
In summary, a method for balancing cost performance and versatility and achieving the best effect is undoubtedly of great economic value.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a pulsed spray evaporation flame synthesis method and apparatus, which are intended to at least partially solve at least one of the above mentioned technical problems.
As one aspect of the present invention, there is provided a pulse type spray evaporation flame synthesis method, comprising the steps of:
injecting the precursor solution into the flame for reaction by pulse atomization, forming a prefabricated material core by the precursor in the precursor solution, and depositing to obtain the final product.
As another aspect of the present invention, there is also provided a pulse type spray evaporation flame synthesis apparatus, including:
the pulse type spray evaporator is used for performing pulse type atomization on the precursor solution;
the burner is connected with the pulse type spray evaporator and used for generating flame so as to enable the pulse type atomized sample precursor solution to react in the flame;
and the collector is used for collecting a final product obtained by forming a pre-prepared material core and depositing the precursor in the precursor solution.
Based on the technical scheme, compared with the prior art, the invention has at least one or part of the following beneficial effects:
(1) the invention combines a pulse type spray evaporator (PSE) with a flame spray pyrolysis method, and accurately adjusts the concentration of a precursor in a liquid raw material and the spraying frequency and the opening time of a spray nozzle (namely, the flow of the precursor is adjusted), thereby controlling the thickness of a membrane, the stoichiometry of a catalyst and the growth rate; meanwhile, the performance reduction of the device caused by the concentration fluctuation of the precursor solution is avoided, and the cost is not increased;
(2) the method has the advantages of low cost, high yield, simple process, easy large-scale production, high activity of the synthesized catalyst, good selectivity and good stability.
Drawings
FIG. 1 is a schematic flow chart of a pulsed spray evaporation flame synthesis method according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a pulsed spray evaporation flame synthesis apparatus according to an embodiment of the present invention;
FIG. 3 is a schematic bottom view of a burner according to an embodiment of the invention;
fig. 4 is a schematic top view of a burner according to an embodiment of the invention.
In the above figures, the reference numerals have the following meanings:
1. 2, 3, 4-flow controller; 5. 6-safety valve; 7-a storage box; 8-a spray nozzle; 9-a pulse generator; 10-heating a belt; 11-a burner; 12-flame; 13-granules; 14-the final product; 15-a substrate; 16-a scaffold; 17-a water pump; 18-a water inlet valve; 19-a water outlet valve; 20-a sample inlet; 21-sample outlet; 22-a fuel gas inlet; 23-a fuel gas outlet; 24-bath gas inlet; 25-bath gas outlet; 26-inlet and outlet of cooling tube.
Detailed Description
The invention provides a novel flame spray pyrolysis method, which is used for synthesizing films or nanoparticles with strong stability and high activity. Meanwhile, the invention also provides a pulse type spray evaporation flame synthesis device for realizing the method.
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
As one aspect of the present invention, there is provided a pulse type spray evaporation flame synthesis method, comprising the steps of:
injecting the precursor solution into the flame for reaction by pulse atomization, forming a prefabricated material core by the precursor in the precursor solution, and depositing to obtain the final product.
In the embodiment of the invention, a precursor solution is sprayed into flame in a droplet state sample formed by atomization, the precursor is combusted in the flame, and the precursor is subjected to a pyrolysis reaction to form a pre-prepared material core; the pre-prepared material core can be understood as powder formed by flame pyrolysis of a precursor in a precursor solution; the powder is deposited to obtain the final product.
In the embodiment of the invention, pulse type atomization sample injection is adopted, so that the concentration of the sample injection of the precursor solution is ensured to be stable, and the final product has uniform shape.
In embodiments of the present invention, the pyrolysis reaction may be an oxidation reaction or a hydrolysis reaction, and the metal oxide is produced by the pyrolysis reaction.
In an embodiment of the invention, the final product comprises a film-like or nanoparticulate substance.
In embodiments of the invention, the final product may be a film-like material or a nanoparticulate material; the film-like structure or the nanoparticle-like structure can be controlled by controlling the average deposition rate and the deposition time.
In the embodiment of the invention, the thickness, the stoichiometry and the growth rate of the final product are controlled by the radio frequency and the pulse width of pulse type atomized feeding,
in the embodiment of the invention, the radio frequency of the pulse type atomization sample introduction mode is less than 100 Hz; for example 50Hz, 30Hz, 10Hz, 5Hz, 1 Hz.
In an embodiment of the present invention, the pulse width is on the order of milliseconds; such as 1 millisecond, 2 milliseconds, 5 milliseconds, 8 milliseconds, 10 milliseconds, 50 milliseconds.
In the embodiment of the invention, the radio frequency and the pulse width are set to be suitable for the final product, wherein the thickness is between nanometer and micrometer, and the weight is milligram.
In an embodiment of the invention, the material of the final product comprises a noble metal oxide, a transition metal oxide or a perovskite.
In an embodiment of the present invention, the material of the final product includes one or more of iridium oxide, palladium oxide, ruthenium oxide, rhodium oxide, iron oxide, cerium oxide, aluminum oxide, chromium oxide, barium oxide, zinc oxide, lanthanum cobalt oxide, and lanthanum manganese oxide.
In an embodiment of the invention, the precursor solution comprises a precursor and a flammable solvent.
In embodiments of the present invention, flammable solvents include, but are not limited to, ethanol; other alcohol solvents can be used, but the ethanol has good stability and is cheap and easy to obtain.
In an embodiment of the invention, the precursor comprises one or more of iridium acetylacetonate, palladium acetate, ruthenium acetate, rhodium acetylacetonate, iron acetylacetonate, cerium acetylacetonate, aluminum acetylacetonate, chromium acetylacetonate, barium acetylacetonate, zinc acetylacetonate hydrate, lanthanum acetylacetonate hydrate, cobalt acetylacetonate, manganese acetylacetonate, lanthanum acetate hydrate.
When the prepared material film or particle is a multi-metal compound, preparing a mixed solution by adopting a plurality of precursors;
wherein the concentration of the precursor is in the order of millimoles per liter, e.g. 1 millimole per liter, 10 millimoles per liter, 20 millimoles per liter, 100 millimoles per liter, 500 millimoles per liter.
In the embodiment of the invention, according to the difference of the kind and structure of the final product to be prepared, the corresponding precursor is selected and dissolved in the flammable solvent to prepare the precursor solution with the mM-level concentration. For example, iron acetylacetonate (Fe (acac)3) Or cobalt acetylacetonate (Co (acac)3) Dissolving in ethanol solution to prepare precursor solution needed by synthesizing the iron-based or copper-based oxide material.
In the embodiment of the invention, before injecting the precursor solution into the flame for reaction by pulse atomization, an oxidant is added into the sample injected by pulse atomization.
In the embodiment of the present invention, the oxidant includes air, but is not limited to this, and may also be oxygen, or a mixture of oxygen and air mixed in a certain ratio. In the examples of the present invention, O2As an oxidant, the burning rate of the droplets can be increased and the final product can be left at a higher temperature for a longer period of time. Furthermore, by measuring the flame spray temperature, it was found that O was used2The specific surface area of the final product synthesized as an oxidizing agent is smaller than that of the final product synthesized using air as an oxidizing agent.
In the reaction process of spraying the solution into the flame, the method also comprises the step of spraying fuel, bath gas and the pulse type atomized sample precursor solution into the flame together;
in embodiments of the invention, the fuel comprises a gaseous or liquid fuel; a mixture of an alkane such as methane and the like and oxygen.
In an embodiment of the present invention, the bath gas may include nitrogen, but is not limited thereto, and may be other inert gas such as argon.
In the embodiment of the present invention, the gas species may be replaced as the case may be. The flow rate of each gas is controlled by a flow controller to achieve a proper flame.
In the embodiment of the invention, the flame height is 5-15 cm; the temperature range is 1500-2000 ℃.
In an embodiment of the invention, solvent evaporation in the precursor solution is instantaneously simultaneous with precursor pyrolysis in the flame. The flame height and the flame temperature are important factors influencing the particle size, the specific surface area, the morphology, the crystal form and other structures of the final product formed after the pyrolysis of the precursor.
In the embodiment of the invention, pulse type atomization sampling is combined, and the height of the flame is suitably 5-15 cm; the temperature range is suitably 1500-2000 ℃.
As another aspect of the present invention, there is also provided a pulse type spray evaporation flame synthesis apparatus, including:
the pulse type spray evaporator is used for performing pulse type atomization on the precursor solution;
the burner is connected with the pulse type spray evaporator and used for generating flame so as to enable the pulse type atomized sample-fed precursor solution to react in the flame;
and the collector is used for collecting a final product obtained by forming a pre-prepared material core and depositing the precursor in the precursor solution.
In an embodiment of the invention, a pulsed spray evaporator comprises a spray nozzle, an evaporation tube and a pulse generator;
the pulse generator is connected with the spray nozzle and used for controlling the spray nozzle to perform pulse type atomization sampling;
a spray nozzle comprising a spray nozzle outlet; the outlet of the spray nozzle is connected with one end of the evaporation tube;
the other end of the evaporating pipe is connected with the burner.
In the embodiment of the invention, the evaporation tube is arranged between the spray nozzle and the burner, so that the spraying frequency of the precursor solution and the opening time of the spray nozzle can be conveniently controlled, and further the thickness, the stoichiometry, the growth rate and the like of a final product can be controlled.
In an embodiment of the invention, the apparatus is combined with a pulsed spray evaporation flame synthesis method, and due to the currently used pulsed spray evaporator, the droplet size of the precursor solution entering the burner is limited; different spray nozzle diameters can be used to meet operating requirements to overcome this limitation with different requirements for pulse frequency and droplet diameter.
In an embodiment of the invention, the apparatus further comprises a heating tape wound on the outer wall of the evaporation tube.
In other embodiments of the invention, the spray nozzles and the pulse generator may be arranged in sets, each set of spray nozzles emitting a different precursor solution, in order to obtain a final product with a multilayer or superlattice structure.
In an embodiment of the present invention, the apparatus further includes an oxidant line, the oxidant line is communicated with the evaporation tube, and is used for conveying the oxidant to the evaporation tube.
In the embodiment of the invention, the oxidant pipeline is communicated with the evaporation pipe, on one hand, the oxidant and the atomized sample are fully mixed, and the oxidant is used as a reaction raw material, which is beneficial to uniform combustion reaction in subsequent flame; on the other hand, the spraying of the oxidant further breaks up the liquid drops of the atomized sample, and further assists in atomization; in yet another aspect, the flow of the oxidizing agent through the evaporator tube also facilitates the transport of the atomized sample through the evaporator tube.
In an embodiment of the present invention, a burner includes a burner body including:
the central channel is arranged at the central shaft of the burner body, one end of the central channel is connected with the evaporation tube, the other end of the central channel is provided with a sample outlet, and the sample outlet is communicated with the flame generation side of the burner body;
the fuel gas channel, one end of the fuel gas channel has fuel gas inlets, another end of the fuel gas channel has fuel gas outlets, the fuel gas outlet communicates with flame generation side of the burner; the fuel gas outlet of the fuel gas channel is annularly arranged along the periphery of the central channel;
one end of the bath gas channel is provided with a bath gas inlet, the other end of the bath gas channel is provided with a bath gas outlet, and the bath gas outlet is communicated with the flame generation side of the burner; the bath gas outlet of the bath gas channel is annularly arranged along the periphery of the fuel gas outlet.
In an embodiment of the invention, the burner further comprises a cooling pipe arranged in the inner space of the burner body and used for cooling the burner; the inlet and the outlet of the cooling pipe are respectively connected with a connecting pipe for forming a circulating flow path, and a water pump, a water tank and a control valve are arranged on the connecting pipe.
In an embodiment of the invention, the apparatus further comprises a fuel gas supply pipe connected to the fuel gas inlet; a safety valve is arranged on the fuel gas supply pipe; the bath gas supply pipe is communicated with the bath gas inlet.
In the embodiment of the invention, a plurality of branch gas supply pipes are arranged on one side of the fuel gas supply pipe, which is opposite to the fuel gas inlet end; each branch gas supply pipe is provided with a flow controller;
the bath gas supply pipe is provided with a flow controller.
In an embodiment of the invention, the collector comprises a substrate and a support, the substrate being disposed on the support; the support is opposite to the outlet of the combustor;
in embodiments of the present invention, the substrate may be a stainless steel mesh, but is not limited thereto, and may also be a metal mesh, a metal sheet, a tin foil, or glass, as long as it is a non-catalytic or non-reactive surface.
In an embodiment of the invention, the apparatus further comprises a stopper arranged between the burner and the collector for directional deposition of the final product on the substrate.
The technical solution of the present invention is further described below with reference to specific examples, but it should be noted that the following examples are only for illustrating the technical solution of the present invention, but the present invention is not limited thereto.
As shown in fig. 1, the method of the present invention comprises the steps of:
(1) and preparing a precursor solution.
(2) Fuel and bath gas injection. The fuel and the bath gas are regulated into the burner by respective flow controllers.
(3) Pulse type atomization sample introduction of the precursor solution. The step (2) is carried out simultaneously. Atomizing the precursor solution prepared in the step (1) by using a spray nozzle provided with a pulse generator, and feeding the atomized precursor solution into a combustion chamber, and adding an oxidant into the atomized precursor solution. And (3) combusting the fuel and the fuel in the step (2) to generate flame.
(4) The flame and the precursor evaporate. And (3) combusting the fuel, the bath gas, the oxidant and the precursor solution in the steps (2) and (3), simultaneously evaporating the precursor solution in the flame to form a prefabricated material core, and then performing coalescence and growth. Influenced by the solvent used in step (3) and the flow rate of the gas in step (2).
(5) Deposition of thin films or particles. The resulting powder is deposited as a thin film or nanoparticles on a substrate on a bottom support.
(6) And (5) collecting the materials. The film deposited on the substrate is taken directly off and the particulate material deposited on the substrate needs to be scraped off for collection.
(7) The thickness, stoichiometry and growth rate of the catalyst thin film obtained in step (5) can be controlled by adjusting the precursor concentration in the liquid raw material and the spray frequency and opening time of the spray nozzle in step (3).
The liquid raw material is maintained at room temperature, and no obvious thermal degradation occurs at the temperature, so that the repeatability of the film growth process is better.
(8) The nanoparticles or thin films obtained in steps (5) (6) may be noble metal oxides, transition metal oxides or perovskites, such as iridium oxide, palladium oxide, ruthenium oxide, rhodium oxide, iron oxide, cerium oxide, aluminum oxide, chromium oxide, zinc oxide, lanthanum cobalt oxide, lanthanum manganese oxide, depending on the reactants.
The invention also provides a pulse type spray evaporation flame synthesis device. As shown in fig. 2, 3 and 4, the device comprises five parts of a gas supply unit, a liquid vaporization sampling unit, a combustion unit, a cooling unit and a film/particle collection unit:
(1) the gas supply unit comprises four gases, oxidant 1, oxidant 2, fuel gas and protective gas, which can be air, O2，CH4And N2And the replacement can be carried out according to the actual situation. Each gas supply pipe is responsible for feeding four gases into the burner, and each gas supply pipe is provided with a flow controller, such as the flow controllers 1, 2, 3 and 4; the individual flow controllers may be adjusted manually or by a control unit.
(2) The liquid vaporization sampling unit comprises a liquid raw material storage tank 7, a spray nozzle 8, a pulse generator 9 and an evaporation tube, wherein a heating tape 10 is wound on the evaporation tube.
(3) The combustion unit comprises a burner 11. The burner comprises a burner body, the burner body comprises a central channel which is arranged at the central shaft of the burner body, one end of the central channel is provided with a sample inlet 20 which is connected with the evaporation tube, the other end of the central channel is provided with a sample outlet 21, and the sample outlet 21 is communicated with the flame generation side of the burner body;
a fuel gas channel, one end of which is provided with a fuel gas inlet 22, the other end of which is provided with a fuel gas outlet 23, and the fuel gas outlet 23 is communicated with the flame generation side of the burner; the fuel gas outlet 23 of the fuel gas channel is annularly arranged along the periphery of the central channel;
one end of the bath gas channel is provided with a bath gas inlet 24, the other end of the bath gas channel is provided with a bath gas outlet 25, and the bath gas outlet 25 is communicated with the flame generation side of the burner; the bath gas outlet 25 of the bath gas passage is annularly arranged along the periphery of the fuel gas outlet 23.
In an embodiment of the present invention, the burner further comprises a cooling pipe disposed in the inner space of the burner for cooling the burner; the inlet and outlet 26 of the cooling pipe are connected to connection pipes, respectively, for forming a circulation flow path, and a water pump, a water tank, and a control valve are provided on the connection pipes.
The burner 11 includes a central passage, a bath gas passage, a fuel gas passage, and a cooling pipe. The precursor flows out of the central passage of the burner 11 and the dispersed fuel gas flows out of the fuel gas outlet 23 (annular gap) of the fuel gas passage. The bath gas is ejected from the bath gas outlet 25. The burner body is made of stainless steel and silicon dioxide, and has good thermal stability, chemical stability, high temperature resistance and acid corrosion resistance. Two safety valves (safety valve 5 and safety valve 6) are installed on the methane and oxygen supply pipe to prevent the reverse flow of the flame 12 into the methane and oxygen supply pipe.
(4) The cooling unit comprises a water pump 17 and an inlet valve 18, an outlet valve 19 and a connecting pipe equipped with the water pump.
(5) The particle collection unit comprises the newly formed particles 13, the deposited end product 14, i.e. the film or nanoparticles, the substrate 15 and the support 16.
Example 1
With iron acetylacetonate (Fe (acac)3) Dissolving the precursor solution in an ethanol solution to prepare a precursor solution required by synthesizing the iron-based oxide material, wherein the concentration of the precursor solution is as follows: 0.02-0.5M;
the spraying frequency of the spraying nozzle is 25-50 Hz, and the opening time is 2-10 ms;
obtaining an iron oxide film layer product with the film thickness of 50-150 mu m and the nano-particle size of 10-30 nm.
Example 2
With cobalt acetylacetonate (Co (acac)3) Dissolving the cobalt-based oxide material in an ethanol solution to prepare a precursor solution required by synthesis of the cobalt-based oxide material, wherein the concentration of the precursor solution is as follows: 0.02-0.5M;
the spraying frequency of the spraying nozzle is 10-25 Hz, and the opening time is 2-10 ms;
obtaining a granular cobalt oxide product with the nano-particle size of 30-45 nm.
Comparative example 1
With iron acetylacetonate (Fe (acac)3) As a precursor, an iron oxide catalyst was prepared by a sol-gel method. The obtained particle size is in the range of 40-70 nm.
Comparative example 2
With iron acetylacetonate (Fe (acac)3) The same iron oxide prepared by a wet impregnation method is used as a precursor, and the particle size of the iron oxide is 80-100 nm.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A pulse type spray evaporation flame synthesis method is characterized by comprising the following steps:
injecting the precursor solution into flame for reaction by pulse atomization, forming a prefabricated material core by the precursor in the precursor solution, and depositing to obtain the final product.
2. The method of claim 1, wherein the pulsed atomization and evaporation flame synthesis method is characterized in that the pulsed atomization and sampling mode has a radio frequency of less than 100 Hz; the pulse width is in the order of milliseconds.
3. The pulsed spray evaporation flame synthesis method of claim 1,
the final product comprises a membranous or nanoparticulate substance;
the final product has a thickness magnitude between nanometer and micrometer and a weight magnitude of milligram;
the material of the final product comprises noble metal oxide, transition metal oxide or perovskite.
4. The pulsed spray evaporation flame synthesis method of claim 3,
the final product is made of one or more of iridium oxide, palladium oxide, ruthenium oxide, rhodium oxide, iron oxide, cerium oxide, aluminum oxide, chromium oxide, barium oxide, zinc oxide, lanthanum cobalt oxide and lanthanum manganese oxide.
5. The pulsed spray evaporation flame synthesis method of claim 1,
the precursor solution comprises a precursor and a flammable solvent;
the flammable solvent includes ethanol;
the precursor comprises one or more of iridium acetylacetonate, palladium acetate, ruthenium acetate, rhodium acetylacetonate, iron acetylacetonate, cerium acetylacetonate, aluminum acetylacetonate, chromium acetylacetonate, barium acetylacetonate, zinc acetylacetonate hydrate, lanthanum acetylacetonate hydrate, cobalt acetylacetonate hydrate, manganese acetylacetonate hydrate and lanthanum acetate hydrate;
wherein the concentration of the precursor is in millimole per liter order.
6. The method as claimed in claim 1, wherein before the step of injecting the precursor solution into the flame for reaction, the method further comprises:
adding an oxidant into a sample injected by pulse atomization;
wherein the oxidant comprises air or oxygen.
7. The pulsed spray evaporation flame synthesis method of claim 1,
the injecting into the flame to react further comprises:
injecting fuel and a bath gas simultaneously into the flame;
wherein the fuel comprises a gaseous or liquid fuel;
the bath gas comprises nitrogen or argon.
The height of the flame is 5-15 cm; the temperature range is 1500-2000 ℃.
8. A pulsed spray evaporative flame synthesis apparatus, comprising:
the pulse type spray evaporator is used for performing pulse type atomization on the precursor solution;
the burner is connected with the pulse type spray evaporator and used for generating flame so as to enable the pulse type atomized sample precursor solution to react in the flame;
and the collector is used for collecting a final product obtained by forming a pre-prepared material core and depositing the precursor in the precursor solution.
9. A pulsed spray evaporation flame synthesis apparatus according to claim 8,
the pulse type spray evaporator comprises a spray nozzle, an evaporation pipe and a pulse generator;
the pulse generator is connected with the spray nozzle and used for controlling the spray nozzle to perform pulse type atomization sampling;
a spray nozzle comprising a spray nozzle outlet; the outlet of the spray nozzle is connected with one end of the evaporation tube;
the other end of the evaporation pipe is connected with the combustor.
10. A pulsed spray evaporation flame synthesis apparatus according to claim 9,
wherein the apparatus further comprises: the oxidant pipeline is communicated with the evaporation pipe and is used for conveying an oxidant into the evaporation pipe;
wherein the burner comprises: a burner body, the burner body comprising: the central channel is arranged at the central shaft of the burner body, one end of the central channel is connected with the evaporation tube, the other end of the central channel is provided with a sample outlet, and the sample outlet is communicated with the flame generation side of the burner body; the fuel gas channel is provided with a fuel gas inlet at one end and a fuel gas outlet at the other end, and the fuel gas outlet is communicated with the flame generation side of the burner; the fuel gas outlet of the fuel gas channel is annularly arranged along the periphery of the central channel; one end of the bath gas channel is provided with a bath gas inlet, the other end of the bath gas channel is provided with a bath gas outlet, and the bath gas outlet is communicated with the flame generation side of the burner; the bath gas outlet of the bath gas channel is annularly arranged along the periphery of the fuel gas outlet;
the combustor also comprises a cooling pipe which is arranged in the inner space of the combustor body and used for cooling the combustor; the inlet and the outlet of the cooling pipe are respectively connected with a connecting pipe for forming a circulating flow path, and a water pump, a water tank and a control valve are arranged on the connecting pipe;
wherein the apparatus further comprises: the fuel gas supply pipe is connected with the fuel gas inlet; a safety valve provided on the fuel gas supply pipe; a bath gas supply pipe connected to the bath gas inlet;
wherein, one side of the fuel gas supply pipe, which is opposite to the fuel gas inlet end, is provided with a plurality of branch gas supply pipes;
wherein, each branch gas supply pipe is provided with a flow controller;
wherein, a flow controller is arranged on the bath gas supply pipe;
wherein the apparatus further comprises: the heating belt is wound on the outer wall of the evaporation tube;
wherein the collector comprises a substrate and a support, the substrate being disposed on the support;
wherein the substrate comprises a stainless steel mesh, a metal sheet, a tin foil sheet or glass;
wherein the apparatus further comprises a stopper disposed between the burner and the collector for directionally depositing the final product on the substrate.
CN202011499440.8A 2020-12-17 2020-12-17 Pulse type spray evaporation flame synthesis method and device Pending CN112717848A (en)

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