CN115418256B - Fuel microsphere, preparation method thereof and propellant - Google Patents

Fuel microsphere, preparation method thereof and propellant Download PDF

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Publication number
CN115418256B
CN115418256B CN202211159703.XA CN202211159703A CN115418256B CN 115418256 B CN115418256 B CN 115418256B CN 202211159703 A CN202211159703 A CN 202211159703A CN 115418256 B CN115418256 B CN 115418256B
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phase solution
chitosan
fuel
boron particles
metal
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CN115418256A (en
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潘伦
邹吉军
薛康
李怀宇
史成香
张香文
王涖
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Tianjin University
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Tianjin University
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00Solid fuels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/10Treating solid fuels to improve their combustion by using additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/30Nuclear fission reactors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a fuel microsphere, a preparation method thereof and a propellant. The fuel microsphere includes: boron particles having a particle diameter of nanometer scale; and chitosan, wherein the chitosan is coated on the surface of the boron particles. The introduction of the organic matter chitosan can lead the nanoscale boron particles in the fuel to exist in the form of microspheres in the storage process, and the boron particles participate in the combustion reaction in the nanoscale in the combustion process, so that the fuel microspheres not only keep the low ignition temperature of the boron particles, but also prevent the agglomeration of products in the combustion process, and can also effectively avoid the reaction of the boron particles with oxygen and water in the air, thereby improving the combustion efficiency and the combustion rate of the boron particles.

Description

Fuel microsphere, preparation method thereof and propellant
Technical Field
The invention relates to the technical field of chemical industry, in particular to a fuel microsphere, a preparation method thereof and a propellant.
Background
Boron has a relatively high volumetric heating value (137.45 MJ/L) and a mass heating value (58.74 MJ/kg) and is considered to be an ideal ramjet solid fuel. However, the boron combustion products have the characteristics of low melting point and high boiling point, so that liquid boron oxide is generated in the combustion process, and the boron and the oxidant are difficult to react. Meanwhile, compared with other metal fuels, boron has the defects of high ignition temperature, low combustion rate and the like.
The nano-boron particles have a lower ignition temperature and a higher burn rate than conventional micro-boron particles. However, the nano boron particles are extremely easy to agglomerate in the storage process due to the high surface energy, and react with oxygen and water in the air to cause difficult ignition and deteriorated combustion of the nano boron particles, and the nano boron particles often need to be modified. However, the current modification results of nano boron particles still cannot meet the requirements, and the invention is particularly proposed in view of the above.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a fuel microsphere, in which the nano-scale boron particles in the fuel exist in microsphere form during storage, and the nano-scale boron particles participate in combustion reaction during combustion, so that the fuel microsphere maintains low ignition temperature of the boron particles, prevents agglomeration of products during combustion, and can effectively avoid reaction of the boron particles with oxygen and water in air, thereby improving combustion efficiency and combustion rate of the boron particles.
In one aspect of the present invention, there is provided a fuel microsphere comprising:
boron particles having a particle diameter of nanometer scale;
and chitosan, wherein the chitosan is coated on the surface of the boron particles.
Further, the fuel microsphere further comprises:
a metal combustion-promoting catalyst adsorbed on the surface of the chitosan;
the metal combustion promoting catalyst comprises at least one of acetylacetone metal salt, metal nitrate and metal sulfate;
and/or the metal acetylacetonate comprises at least one of molybdenum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and lead acetylacetonate;
and/or the metal nitrate comprises at least one of ferric nitrate, cobalt nitrate, nickel nitrate and lead nitrate;
and/or the metal sulfate comprises at least one of ferric sulfate, cobalt sulfate, nickel sulfate and lead sulfate;
and/or the mass of the metal combustion promoting catalyst is 4-10wt% of the mass of the boron particles.
Further, the diameter of the fuel microsphere is 10-40 μm;
and/or the chitosan content is 5-50wt%, based on the total mass of the fuel microsphere;
and/or the particle size of the boron particles is 50-80nm.
In another aspect of the present invention, there is provided a method for preparing the fuel microsphere described above, comprising:
coating chitosan on the surface of the boron particles to obtain the fuel microsphere.
Further, the preparation method of the fuel microsphere further comprises the following steps:
and adsorbing a metal combustion promoting catalyst on the surface of the chitosan to obtain the fuel microsphere.
Further, coating the chitosan on the surface of the boron particles comprises:
s11, dispersing the boron particles into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution;
s12, introducing the disperse phase solution and the continuous phase solution prepared in the step S11 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets;
s13, introducing the monodisperse droplets obtained in the step S12 into the receiving phase solution in the step S11, and reacting to obtain the fuel microspheres;
and/or the monodisperse droplets obtained in step S12 have a diameter of 18.5 to 108 μm.
Further, the concentration of boron particles in the dispersed phase solution prepared in the step S11 is 1-5wt%, the concentration of chitosan is 0.5-1wt%, and the concentration of acetic acid is 1-2wt%; the concentration of span-80 in the continuous phase solution is 1-3wt%; the concentration of glutaraldehyde in the receiving phase solution is 1-3wt%;
and/or, in the step S12, the disperse phase solution is introduced into the droplet microfluidic device at a flow rate of 5-10 mu L/min;
and/or, in the step S12, the continuous phase solution is introduced into the droplet microfluidic device at a flow rate of 10-100 mu L/min.
Further, adsorbing a metal-promoting catalyst on the surface of the chitosan comprises:
s21, dispersing the boron particles and the metal combustion promoting catalyst into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution;
s22, introducing the disperse phase solution and the continuous phase solution prepared in the step S21 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets;
s23, introducing the monodisperse droplets obtained in the step S22 into the receiving phase solution in the step S21, and reacting to obtain the fuel microspheres;
and/or the monodisperse droplets obtained in step S22 have a diameter of 18.5 to 108 μm.
Further, adsorbing a metal-promoting catalyst on the surface of the chitosan comprises:
s31, coating the chitosan on the surface of the boron particles to obtain an intermediate product;
s32, dispersing the intermediate product into an aqueous solution containing the metal combustion promoting catalyst, and adsorbing to obtain the fuel microsphere.
In another aspect of the invention, the invention provides a propellant comprising the fuel microspheres described hereinbefore.
Compared with the prior art, the invention has at least the following beneficial effects:
the nano-scale boron particles in the fuel can exist in the form of microspheres in the storage process by introducing the organic chitosan, so that the monodispersion of the fuel microspheres is realized, and the problem of boron particle agglomeration is effectively solved; the chitosan can generate a large amount of gas in the combustion process, so that boron particles participate in the combustion reaction again in the nano scale in the combustion process, and therefore, the fuel microspheres not only keep the low ignition temperature of the boron particles, but also prevent the agglomeration of products in the combustion process, and the existence of the chitosan can also effectively prevent the boron particles from reacting with oxygen and water in the air, thereby improving the combustion efficiency and the combustion rate of the boron particles; in addition, the fuel microsphere has low ignition temperature, high combustion efficiency and controllable size.
Drawings
Fig. 1 is a schematic diagram of a process for synthesizing monodisperse droplets using a microfluidic device.
FIG. 2 is a schematic illustration of the process for preparing monodisperse droplets of examples 1-5.
FIG. 3 is a distribution diagram of the particle diameters of monodisperse droplets in examples 1 to 15.
Fig. 4 is an SEM (scanning electron microscope) image of the fuel microspheres of examples 2, 16, 17, 18 and the fuel of comparative example 1.
FIG. 5 is an optical image of the fuel microspheres of examples 19, 20, 21.
FIG. 6 is a graph showing particle size distribution of fuel microspheres of examples 2, 16, 17, 18, 19, 20, and 21.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect of the present invention, there is provided a fuel microsphere comprising:
boron particles having a particle diameter of nanometer scale;
and chitosan, wherein the chitosan is coated on the surface of the boron particles.
The nano-scale boron particles in the fuel can exist in the form of microspheres in the storage process by introducing the organic chitosan, so that the monodispersion of the fuel microspheres is realized, and the problem of boron particle agglomeration is effectively solved; the chitosan can generate a large amount of gas in the combustion process, so that boron particles participate in the combustion reaction again in the nano scale in the combustion process, and therefore, the fuel microspheres not only keep the low ignition temperature of the boron particles, but also prevent the agglomeration of products in the combustion process, and the existence of the chitosan can also effectively prevent the boron particles from reacting with oxygen and water in the air, thereby improving the combustion efficiency and the combustion rate of the boron particles; in addition, the fuel microsphere has low ignition temperature, high combustion efficiency and controllable size.
In some embodiments of the invention, the fuel microsphere further comprises: the metal combustion-promoting catalyst can coordinate with lone pair electrons of nitrogen atoms in chitosan molecules, so that the metal combustion-promoting catalyst is adsorbed on the surface of the chitosan; the metal-promoted catalyst comprises at least one of a metal acetylacetonate, a metal nitrate, and a metal sulfate. Therefore, the adsorption of the chitosan to the metal combustion-promoting catalyst realizes the low load and uniform distribution of the metal combustion-promoting catalyst in the fuel microspheres; in the combustion process, the metal catalyst has an interface catalysis effect on the surface of nB (nano-scale boron particles) and is coupled with a micro-explosion process initiated by chitosan combustion, so that the obtained fuel microsphere further reduces the ignition temperature of the boron particles, solves the problem of agglomeration of the nano-scale boron particles, and further improves the combustion efficiency and the combustion rate of the boron particles.
In some embodiments of the invention, the metal acetylacetonate comprises at least one of molybdenum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, and lead acetylacetonate; the metal nitrate comprises at least one of ferric nitrate, cobalt nitrate, nickel nitrate and lead nitrate; the metal sulfate includes at least one of ferric sulfate, cobalt sulfate, nickel sulfate, and lead sulfate.
In some embodiments of the invention, the mass of the metal-promoted catalyst is 4-10wt% (e.g., may be 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc.) of the mass of the boron particles. With respect to the above content range, when the content of the metal-promoting catalyst is too high, the theoretical heat value of the microspheres decreases, and when the content of the metal-promoting catalyst is too low, the promoting effect of the metal-promoting catalyst decreases.
In some embodiments of the invention, the chitosan is present in an amount of 5-50wt% (e.g., may be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, etc.), based on the total mass of the fuel microsphere. When the content of chitosan is too low, relative to the above content range, no fuel microspheres can be formed; when the chitosan content is too high, both the theoretical heat value and the combustion heat value of the fuel microspheres are reduced.
The term "microsphere" as used herein refers to a sphere having a particle diameter of micrometer scale, and has uniformity of size and a coefficient of variation of less than 5%. In some embodiments of the invention, the fuel microspheres have a diameter of 10-40 μm.
In some embodiments of the invention, the boron particles have a particle size of 50-80nm.
In some embodiments of the invention, the fuel microspheres are used in a TG-DSC (thermogravimetric analysis combined with differential scanning calorimetry) thermogravimetric analysis test, which significantly reduces the ignition temperature of the boron particles under air conditions.
In other embodiments of the invention, the fuel microspheres are used in an oxygen bomb calorimeter combustion test with a heat of combustion of greater than 30MJ/kg and a peak combustion pressure of no less than 4.8MPa under 3MPa oxygen conditions.
In another aspect of the present invention, there is provided a method for preparing the fuel microsphere described above, comprising: coating chitosan on the surface of the boron particles to obtain the fuel microsphere.
It will be appreciated that the chitosan and boron particles are in accordance with the foregoing description and will not be described in further detail herein.
In some embodiments of the invention, the size-controllable monodisperse fuel microspheres are prepared by coating chitosan on the surface of boron particles by adopting a droplet microfluidic technology.
In some embodiments of the invention, the method of preparing a fuel microsphere further comprises: and adsorbing a metal combustion promoting catalyst on the surface of the chitosan to obtain the fuel microsphere.
It will be appreciated that the metal-based catalyst is in accordance with the foregoing description and will not be described in further detail herein.
In some embodiments of the invention, coating the surface of the boron particle with chitosan comprises:
s11, dispersing the boron particles into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution; s12, introducing the disperse phase solution and the continuous phase solution prepared in the step S11 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets; and S13, introducing the monodisperse droplets obtained in the step S12 into the receiving phase solution in the step S11, and reacting to obtain the fuel microspheres. Therefore, n-octanol is adopted as a continuous phase, chitosan dispersion liquid of boron particles is adopted as a disperse phase, monodisperse liquid drops are controllably prepared through a liquid drop microfluidic device, and then the liquid drops are subjected to liquid phase extraction and chemical crosslinking to prepare the fuel microspheres with uniform sizes.
In some embodiments of the invention, the monodisperse droplets obtained in step S12 have a diameter of 18.5-108 μm.
In some embodiments of the present invention, the concentration of boron particles in the dispersed phase solution prepared in step S11 is 1 to 5wt%, the concentration of chitosan is 0.5 to 1wt%, and the concentration of acetic acid is 1 to 2wt%; the concentration of span-80 in the continuous phase solution is 1-3wt%; the concentration of glutaraldehyde in the receiving phase solution is 1-3wt%.
In some embodiments of the invention, in the step S12, the dispersed phase solution is introduced into the droplet microfluidic device at a flow rate of 5 to 10 μl/min; in the step S12, the continuous phase solution is introduced into a droplet microfluidic device at a flow rate of 10-100 mu L/min. Thus, the particle size of the fuel microspheres can be effectively controlled by controlling the flow rates of the dispersed phase solution and the continuous phase solution.
The inventor of the invention discovers that the introduction of the metal combustion promoting catalyst can effectively reduce the ignition temperature of boron particles and improve the combustion rate and the combustion efficiency of the boron particles, however, the existing metal combustion promoting catalyst adding method mostly adopts a mechanical mixing method, the method is simple to operate, but the metal combustion promoting catalyst is difficult to uniformly distribute in the boron particles, meanwhile, the contact area between the metal combustion promoting catalyst and the boron particles is reduced due to the larger metal combustion promoting catalyst particles, so that the combustion rate promoting efficiency is low, the ignition temperature cannot be effectively reduced, and a large amount of metal combustion promoting catalyst is needed to be added to solve the problems, thereby reducing the energy density of fuel. According to the invention, a liquid drop microfluidic technology is adopted to introduce the metal combustion-promoting catalyst into the fuel microsphere, and the low-load and uniform distribution of the metal combustion-promoting catalyst in the fuel microsphere is realized through the adsorption of chitosan to the metal combustion-promoting catalyst.
In some embodiments of the invention, adsorbing a metal-promoting catalyst on the surface of the chitosan comprises: s21, dispersing the boron particles and the metal combustion promoting catalyst into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution; s22, introducing the disperse phase solution and the continuous phase solution prepared in the step S21 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets (the schematic diagram of the synthesis process of the monodisperse droplets is shown in figure 1); and S23, introducing the monodisperse droplets obtained in the step S22 into the receiving phase solution in the step S21, and reacting to obtain the fuel microspheres.
In some embodiments of the invention, the monodisperse droplets obtained in step S22 have a diameter of 18.5-108 μm.
In some embodiments of the present invention, the concentration of boron particles in the dispersed phase solution prepared in step S21 is 1 to 5wt%, the concentration of chitosan is 0.5 to 1wt%, and the concentration of acetic acid is 1 to 2wt%; the concentration of span-80 in the continuous phase solution is 1-3wt%; the concentration of glutaraldehyde in the receiving phase solution is 1-3wt%; the content of the metal combustion promoting catalyst is 4-10wt% of the mass of the boron particles.
In some embodiments of the present invention, in the step S22, the dispersed phase solution is introduced into the droplet microfluidic device at a flow rate of 5 to 10 μl/min; in the step S22, the continuous phase solution is introduced into the droplet microfluidic device at a flow rate of 10-100 mu L/min. Thus, the particle size of the fuel microspheres can be effectively controlled by controlling the flow rates of the dispersed phase solution and the continuous phase solution.
In some embodiments of the invention, adsorbing a metal-promoting catalyst on the surface of the chitosan comprises:
s31, coating the chitosan on the surface of the boron particles to obtain an intermediate product;
s32, dispersing the intermediate product into an aqueous solution containing the metal combustion promoting catalyst, and adsorbing to obtain the fuel microsphere.
It will be appreciated that the specific step of coating the surface of the boron particles with the chitosan in step 31 may include the following steps:
1) Dispersing the boron particles into an aqueous solution containing the chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution; the concentration of boron particles in the disperse phase solution prepared in the step 1) is 1-5wt%, the concentration of chitosan is 0.5-1wt% and the concentration of acetic acid is 1-2wt%; the concentration of span-80 in the continuous phase solution is 1-3wt%; the concentration of glutaraldehyde in the receiving phase solution is 1-3wt%;
2) Introducing the disperse phase solution prepared in the step 1) into a droplet microfluidic device at a flow rate of 5-10 mu L/min; introducing the continuous phase solution prepared in the step 1) into a droplet microfluidic device at a flow rate of 10-100 mu L/min to obtain monodisperse droplets with diameters of 18.5-108 mu m;
3) And (2) introducing the monodisperse droplets obtained in the step (2) into the receiving phase solution obtained in the step (1), and reacting to obtain the intermediate product.
In another aspect of the invention, the invention provides a propellant comprising the fuel microspheres described hereinbefore.
It will be appreciated that the propellant may include conventional materials such as binders, curing agents, plasticizers, bonding agents, and the like in addition to the fuel microspheres described above, and will not be described in detail herein.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Examples
Example 1
The preparation method of the fuel microsphere comprises the following steps:
(1) Preparation of dispersed, continuous and receiving phases
Preparation of a dispersed phase: 0.075g (0.75 wt%) chitosan and 0.15g acetic acid are added into 9.475g deionized water, and stirred to obtain clear solution, and 0.3g (3 wt%) nano boron (nB) with particle size of 50-80 nm) is added into the above-mentioned solution, and then ultrasonic treatment is conducted for 3 hr so as to uniformly disperse the above-mentioned solution so as to obtain dispersed phase.
Preparation of the continuous phase: 1.2g (2 wt%) of span-80 was added to 58.8g of n-octanol and stirred to obtain a clear solution, a continuous phase.
Preparation of the receiving phase: a0.5 wt% saturated glutaraldehyde n-octanol solution was added to a 2wt% span-80 n-octanol solution and stirred to obtain a clear solution to obtain a receiving phase.
(2) Preparation of fuel microspheres
As shown in fig. 1, a single channel syringe pump was used to pump the dispersed phase (Q d ) Is injected into a droplet microfluidic device at a flow rate of 5 μl/min, and a continuous phase (Q is injected using a dual channel syringe pump c ) Injecting into a droplet microfluidic device at a flow rate of 10 mu L/min, continuously shearing the disperse phase under continuous phase to form monodisperse droplets with uniform size (the preparation process of the monodisperse droplets is shown in figure 2, the particle size of the monodisperse droplets is shown in figure 3), continuously introducing the droplets into the receiving phase, stirring and solidifying for 12h, and centrifuging, washing and vacuum drying for 12h to obtain the monodisperse fuel microspheres.
Example 2:
the fuel microspheres were prepared substantially as in example 1, except that the continuous phase flow was 20 μl/min; the preparation process of the monodisperse droplets in this example is shown in fig. 2, the particle size of the monodisperse droplets is shown in fig. 3, the SEM image of the fuel microspheres is shown in fig. 4, and the particle size distribution of the fuel microspheres is shown in fig. 6.
Example 3:
the fuel microspheres were prepared substantially as in example 1, except that the continuous phase flow was 30 μl/min; the preparation process of the monodisperse droplets in this example is shown in fig. 2, and the particle size of the monodisperse droplets is shown in fig. 3.
Example 4:
the fuel microspheres were prepared substantially as in example 1, except that the continuous phase flow was 40 μl/min; the preparation process of the monodisperse droplets in this example is shown in fig. 2, and the particle size of the monodisperse droplets is shown in fig. 3.
Example 5:
the fuel microspheres were prepared essentially as in example 1, except that the continuous phase had a flow of 50 μl/min; the preparation process of the monodisperse droplets in this example is shown in fig. 2, and the particle size of the monodisperse droplets is shown in fig. 3.
Example 6:
the fuel microspheres were prepared in substantially the same manner as in example 1, except that the flow rate of the dispersed phase was 7.5. Mu.L/min, the flow rate of the continuous phase was 15. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 7:
the fuel microspheres were prepared in substantially the same manner as in example 6, except that the flow rate of the continuous phase was 30. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 8:
the fuel microspheres were prepared in substantially the same manner as in example 6, except that the flow rate of the continuous phase was 45. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 9:
the fuel microspheres were prepared in substantially the same manner as in example 6, except that the flow rate of the continuous phase was 60. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 10:
the fuel microspheres were prepared in substantially the same manner as in example 6, except that the flow rate of the continuous phase was 75. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 11:
the fuel microspheres were prepared in substantially the same manner as in example 1, except that the flow rate of the dispersed phase was 10. Mu.L/min, and the flow rate of the continuous phase was 20. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 12:
the fuel microspheres were prepared in substantially the same manner as in example 11, except that the flow rate of the continuous phase was 40. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 13:
the fuel microspheres were prepared in substantially the same manner as in example 11 except that the flow rate of the continuous phase was 60. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 14:
the fuel microspheres were prepared in substantially the same manner as in example 11, except that the flow rate of the continuous phase was 80. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 15:
the fuel microspheres were prepared in substantially the same manner as in example 11 except that the flow rate of the continuous phase was 100. Mu.L/min, and the particle size of the monodisperse droplets in this example was as shown in FIG. 3.
Example 16:
the fuel microspheres were prepared in substantially the same manner as in example 2, except that the nano-boron content in the dispersed phase was 2wt%, the SEM image of the fuel microspheres was shown in fig. 4, and the particle size distribution of the fuel microspheres was shown in fig. 6.
Example 17:
the fuel microspheres were prepared in substantially the same manner as in example 2, except that the nano-boron content in the dispersed phase was 4wt%, the SEM image of the fuel microspheres was shown in fig. 4, and the particle size distribution of the fuel microspheres was shown in fig. 6.
Example 18:
the fuel microspheres were prepared in substantially the same manner as in example 2, except that the nano-boron content in the dispersed phase was 5wt%, the SEM image of the fuel microspheres was shown in fig. 4, and the particle size distribution of the fuel microspheres was shown in fig. 6.
Example 19:
the fuel microspheres were prepared in substantially the same manner as in example 17 except that 0.033g of molybdenum acetylacetonate was added to the dispersion phase as a combustion promoting catalyst, the optical image of the fuel microspheres was as shown in FIG. 5, and the particle size distribution of the fuel microspheres was as shown in FIG. 6.
Example 20:
the fuel microspheres were prepared in substantially the same manner as in example 17 except that 0.033g of iron acetylacetonate was added to the dispersion phase as a combustion promoting catalyst, the optical image of the fuel microspheres was as shown in FIG. 5, and the particle size distribution of the fuel microspheres was as shown in FIG. 6.
Example 21:
the fuel microspheres were prepared in substantially the same manner as in example 17 except that 0.033g of cobalt acetylacetonate was added to the dispersed phase as a combustion promoting catalyst, the optical image of the fuel microspheres was as shown in FIG. 5, and the particle size distribution of the fuel microspheres was as shown in FIG. 6.
Comparative example 1
The fuel is nano boron (particle size 50-80 nm), and the SEM image of the fuel is shown in FIG. 4.
Ignition temperature test:
5mg of the fuel microspheres of examples 1-21 and the fuel of comparative example 1 were respectively taken, the thermal properties of the samples were tested by a TG-DSC comprehensive thermal analyzer at a heating rate of 10 ℃/min under an air atmosphere, the test temperature was room temperature to 1000 ℃, the ignition temperature was obtained by a tangential method, and the ignition temperature was as shown in Table 1.
Constant volume combustion and combustion heat value test:
the combustion heat value of the test sample was measured under an oxygen atmosphere of 3MPa using an oxygen bomb calorimeter using 0.15g of fuel (the fuel includes the fuel microspheres of examples 1 to 21 and the fuel of comparative example 1, respectively) while the pressure change of the combustion process was collected. The heat of combustion and the peak maximum pressure of the fuel microspheres of examples 1 to 21 and the fuel of comparative example 1 are shown in table 1.
TABLE 1
The above is not relevant and is applicable to the prior art.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.

Claims (10)

1. A fuel microsphere, comprising:
boron particles having a particle diameter of nanometer scale;
chitosan, wherein the chitosan is coated on the surface of the boron particles;
a metal combustion-promoting catalyst adsorbed on the surface of the chitosan;
the metal combustion promoting catalyst comprises at least one of acetylacetone metal salt, metal nitrate and metal sulfate;
the mass of the metal combustion promoting catalyst is 4-10wt% of the mass of the boron particles;
the diameter of the fuel microsphere is 10-40 mu m;
the content of the chitosan is 5-50wt% based on the total mass of the fuel microsphere;
coating the surface of the boron particles with chitosan comprises:
s11, dispersing the boron particles into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution;
s12, introducing the disperse phase solution and the continuous phase solution prepared in the step S11 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets;
s13, introducing the monodisperse droplets obtained in the step S12 into the receiving phase solution in the step S11, and reacting to obtain the fuel microspheres;
the monodisperse droplets obtained in step S12 have a diameter of 18.5-108 μm.
2. The fuel microsphere according to claim 1, further comprising:
the metal acetylacetonate comprises at least one of molybdenum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and lead acetylacetonate;
and/or the metal nitrate comprises at least one of ferric nitrate, cobalt nitrate, nickel nitrate and lead nitrate;
and/or the metal sulfate comprises at least one of ferric sulfate, cobalt sulfate, nickel sulfate and lead sulfate.
3. The fuel microsphere according to claim 1 or 2, wherein the fuel microsphere comprises a polymer,
the particle size of the boron particles is 50-80nm.
4. A method of preparing the fuel microsphere according to any one of claims 1 to 3, comprising:
coating chitosan on the surface of the boron particles to obtain the fuel microsphere.
5. The method of manufacturing according to claim 4, further comprising:
and adsorbing a metal combustion promoting catalyst on the surface of the chitosan to obtain the fuel microsphere.
6. The method of claim 4 or 5, wherein coating the surface of the boron particles with chitosan comprises:
s11, dispersing the boron particles into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution;
s12, introducing the disperse phase solution and the continuous phase solution prepared in the step S11 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets;
s13, introducing the monodisperse droplets obtained in the step S12 into the receiving phase solution in the step S11, and reacting to obtain the fuel microspheres;
and/or the monodisperse droplets obtained in step S12 have a diameter of 18.5 to 108 μm.
7. The preparation method according to claim 6, wherein the concentration of boron particles in the dispersed phase solution prepared in step S11 is 1-5wt%, the concentration of chitosan is 0.5-1wt%, and the concentration of acetic acid is 1-2wt%; the concentration of span-80 in the continuous phase solution is 1-3wt%; the concentration of glutaraldehyde in the receiving phase solution is 1-3wt%;
and/or, in the step S12, the disperse phase solution is introduced into the droplet microfluidic device at a flow rate of 5-10 mu L/min;
and/or, in the step S12, the continuous phase solution is introduced into the droplet microfluidic device at a flow rate of 10-100 mu L/min.
8. The method of claim 5, wherein adsorbing a metal-promoting catalyst on the surface of the chitosan comprises:
s21, dispersing the boron particles and the metal combustion promoting catalyst into an aqueous solution containing chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into the n-octanol solution containing span-80 to obtain a receiving phase solution;
s22, introducing the disperse phase solution and the continuous phase solution prepared in the step S21 into a droplet microfluidic device at a certain flow rate to obtain monodisperse droplets;
s23, introducing the monodisperse droplets obtained in the step S22 into the receiving phase solution in the step S21, and reacting to obtain the fuel microspheres;
and/or the monodisperse droplets obtained in step S22 have a diameter of 18.5 to 108 μm.
9. The method of claim 5, wherein adsorbing a metal-promoting catalyst on the surface of the chitosan comprises:
s31, coating the chitosan on the surface of the boron particles to obtain an intermediate product;
s32, dispersing the intermediate product into an aqueous solution containing the metal combustion promoting catalyst, and adsorbing to obtain the fuel microsphere.
10. A propellant comprising the fuel microsphere of any one of claims 1 to 3.
CN202211159703.XA 2022-09-22 2022-09-22 Fuel microsphere, preparation method thereof and propellant Active CN115418256B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB627043A (en) * 1946-01-16 1949-07-26 Bataafsche Petroleum Improvements in or relating to the production of round or lachrymiform solid particles of substantially uniform size
CN101624449A (en) * 2009-07-23 2010-01-13 天津大学 Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application
US11203721B1 (en) * 2019-04-26 2021-12-21 Precision Combustion, Inc. Process of removing a metal from a fluid hydrocarbon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB627043A (en) * 1946-01-16 1949-07-26 Bataafsche Petroleum Improvements in or relating to the production of round or lachrymiform solid particles of substantially uniform size
CN101624449A (en) * 2009-07-23 2010-01-13 天津大学 Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application
US11203721B1 (en) * 2019-04-26 2021-12-21 Precision Combustion, Inc. Process of removing a metal from a fluid hydrocarbon

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