CN115418256A - Fuel microsphere, preparation method thereof and propellant - Google Patents
Fuel microsphere, preparation method thereof and propellant Download PDFInfo
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- CN115418256A CN115418256A CN202211159703.XA CN202211159703A CN115418256A CN 115418256 A CN115418256 A CN 115418256A CN 202211159703 A CN202211159703 A CN 202211159703A CN 115418256 A CN115418256 A CN 115418256A
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- fuel
- chitosan
- phase solution
- boron particles
- metal
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- 239000000446 fuel Substances 0.000 title claims abstract description 120
- 239000004005 microsphere Substances 0.000 title claims abstract description 112
- 239000003380 propellant Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 115
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052796 boron Inorganic materials 0.000 claims abstract description 88
- 238000002485 combustion reaction Methods 0.000 claims abstract description 71
- 229920001661 Chitosan Polymers 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 44
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 34
- 230000001737 promoting effect Effects 0.000 claims description 23
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 17
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 87
- 238000009826 distribution Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
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- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS 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
- C10L5/00—Solid fuels
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS 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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (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, the particle size of which is nanometer-scale; chitosan, wherein the chitosan is coated on the surface of the boron particles. The introduction of the organic chitosan can enable the nano-scale boron particles in the fuel to exist in a microsphere form in the storage process, and the boron particles participate in the combustion reaction in the nano-scale manner 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 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
Technical Field
The invention relates to the technical field of chemical industry, in particular to fuel microspheres, a preparation method thereof and a propellant.
Background
Boron has a high volumetric heating value (137.45 MJ/L) and a high mass heat value (58.74 MJ/kg), and is considered to be an ideal solid fuel for a ramjet engine. However, 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 reaction of boron and an oxidant is difficult. Compared with other metal fuels, boron has the defects of high ignition temperature, slow combustion rate and the like.
The nano boron particles have a lower ignition temperature and a higher burning rate than the conventional micro boron particles. However, the nano boron particles are easy to agglomerate during storage due to the high surface energy of the nano boron particles, and simultaneously react with oxygen and water in the air to cause difficult ignition and combustion deterioration of the nano boron particles, so that the nano boron particles are required to be modified. However, the modification result of the nano boron particles still can not meet the requirement at present, and the invention is particularly provided in view of the above.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide a fuel microsphere, the introduction of organic chitosan enables nanometer-scale boron particles in the fuel to exist in a microsphere form in the storage process, and the boron particles participate in a combustion reaction in a nanometer scale in the combustion process, so that the fuel microsphere not only maintains the low ignition temperature of the boron particles, but also prevents the agglomeration of products in the combustion process, and the existence of the chitosan can effectively avoid 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 one aspect of the present invention, there is provided a fuel microsphere comprising:
boron particles, the particle size of which is nanometer-scale;
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 acetylacetone metal salt 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, based on the total mass of the fuel microsphere, the content of the chitosan is 5-50wt%;
and/or the particle size of the boron particles is 50-80nm.
In another aspect of the present invention, the present invention provides a method for preparing the fuel microsphere described above, comprising:
and 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 promotion catalyst on the surface of the chitosan to obtain the fuel microsphere.
Further, coating chitosan on the surface of the boron particle comprises:
s11, 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 an n-octanol solution containing span-80 to obtain a receiving phase solution;
s12, introducing the dispersed 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 liquid drops obtained in the step S12 into the receiving phase solution obtained in the step S11, and reacting to obtain the fuel microspheres;
and/or the diameter of the monodisperse droplet obtained in step S12 is 18.5-108 μm.
Further, 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%;
and/or in the step S12, the dispersed phase solution is introduced into the droplet microfluidic device at a flow rate of 5-10 muL/min;
and/or in the step S12, the continuous phase solution is introduced into the droplet microfluidic device at the flow rate of 10-100 mu L/min.
Further, adsorbing a metal-promoted catalyst on the surface of the chitosan comprises:
s21, dispersing the boron particles and the metal combustion-promoting catalyst 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 an n-octanol solution containing span-80 to obtain a receiving phase solution;
s22, introducing the dispersed phase solution and the continuous phase solution prepared in the step S21 into a droplet microfluidic device at a certain flow rate to obtain a monodisperse droplet;
s23, introducing the monodisperse liquid drops obtained in the step S22 into the receiving phase solution obtained in the step S21, and reacting to obtain the fuel microspheres;
and/or the diameter of the monodisperse droplet obtained in step S22 is 18.5-108 μm.
Further, adsorbing a metal-promoted 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 there is provided a propellant comprising fuel microspheres as hereinbefore described.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
the introduction of the organic chitosan can enable the nano-scale boron particles in the fuel to exist in a microsphere form in the storage process, 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 a nano scale in the combustion process, 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, the existence of the chitosan can also effectively avoid the reaction of the boron particles with oxygen and water in the air, and the combustion efficiency and the combustion rate of the boron particles are improved; 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 diagram of the monodisperse droplet preparation process of examples 1-5.
FIG. 3 is a graph of the particle size distribution of the monodisperse droplets of examples 1-15.
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 micro-spheres of examples 19, 20, 21.
FIG. 6 is a graph of the particle size distribution of the fuel microspheres of examples 2, 16, 17, 18, 19, 20, 21.
Detailed Description
The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides a fuel microsphere comprising:
boron particles, the particle size of which is nanometer-scale;
chitosan, wherein the chitosan is coated on the surface of the boron particles.
The introduction of the organic chitosan can enable the nano-scale boron particles in the fuel to exist in a microsphere form in the storage process, 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 the boron particles participate in the combustion reaction again in the nano scale in the combustion process, 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, the existence of the chitosan can also effectively avoid the reaction of the boron particles and oxygen and water in the air, and the combustion efficiency and the combustion rate of the boron particles are improved; 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 generate coordination with lone-pair electrons of nitrogen atoms in chitosan molecules so as to be adsorbed on the surface of the chitosan; the metal combustion promoting catalyst includes at least one of a metal salt of acetylacetone, a metal nitrate, and a metal sulfate. Therefore, the low-loading amount and uniform distribution of the metal combustion-promoting catalyst in the fuel microspheres are realized through the adsorption of chitosan on the metal combustion-promoting catalyst; in the combustion process, the metal catalyst generates interfacial catalysis on the surface of nB (nano-scale boron particles) and is coupled with the micro-explosion process initiated by the combustion of chitosan, so that the obtained fuel microsphere further reduces the ignition temperature of the boron particles, solves the agglomeration problem 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 metallic acetylacetonate salt 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 ignition catalyst is 4-10wt% (e.g., can be 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%, etc.) of the mass of the boron particles. With respect to the above content range, when the content of the metal combustion promoting catalyst is too high, the theoretical calorific value of the microspheres decreases, and when the content of the metal combustion promoting catalyst is too low, the combustion promoting effect of the metal combustion 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%, or 50wt%, etc.) based on the total mass of the fuel microsphere. With respect to the above content range, when the content of chitosan is too low, fuel microspheres cannot be formed; when the content of chitosan is too high, both the theoretical calorific value and the combustion calorific value of the fuel microspheres are reduced.
It should be noted that the term "microsphere" herein refers to a sphere with a micron-sized particle size, which has a size uniformity and a coefficient of variation of less than 5%. In some embodiments of the invention, the fuel microspheres have a diameter of 10 to 40 μm.
In some embodiments of the invention, the boron particles have a particle size of 50 to 80nm.
In some embodiments of the invention, the fuel microspheres are used in TG-DSC (thermogravimetric analysis coupled with differential scanning calorimetry) thermal analysis tests to significantly reduce the ignition temperature of 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 greater than 30MJ/kg and a peak combustion pressure of no less than 4.8MPa in an oxygen atmosphere of 3 MPa.
In another aspect of the present invention, the present invention provides a method for preparing the fuel microsphere described above, comprising: and coating chitosan on the surface of the boron particles to obtain the fuel microspheres.
It will be appreciated that the chitosan and boron particles are in accordance with the foregoing description and will not be redundantly described here.
In some embodiments of the present invention, the size-controllable monodisperse fuel microsphere is prepared by coating chitosan on the surface of boron particles by droplet microfluidics.
In some embodiments of the present invention, the method of preparing fuel microspheres further comprises: and adsorbing a metal combustion promotion catalyst on the surface of the chitosan to obtain the fuel microsphere.
It is to be understood that the metal-promoted catalyst is consistent with the foregoing description and will not be redundantly described here.
In some embodiments of the invention, coating chitosan on the surface of boron particles comprises:
s11, 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 an n-octanol solution containing span-80 to obtain a receiving phase solution; s12, introducing the dispersed 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, the monodisperse liquid drops obtained in the step S12 are led into the receiving phase solution obtained in the step S11, and the fuel microspheres are obtained after reaction. Therefore, n-octanol is used as a continuous phase, chitosan dispersion liquid of boron particles is used as a dispersed phase, monodisperse liquid drops are controllably prepared through a liquid drop microfluidic control device, and then the liquid drops are prepared into the fuel microspheres with uniform sizes through a liquid phase extraction and chemical crosslinking method.
In some embodiments of the invention, the monodisperse droplet obtained in step S12 has 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 step S12, the dispersed phase solution is introduced into the droplet microfluidic device at a flow rate of 5 to 10 μ L/min; 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. Therefore, the particle size of the fuel microspheres can be effectively controlled by controlling the flow of the dispersed phase solution and the continuous phase solution.
The inventor of the invention finds 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 adding method of the metal combustion promoting catalyst mostly adopts a mechanical mixing method, the method is simple to operate, but the metal combustion promoting catalyst is difficult to be uniformly distributed in the boron particles, and meanwhile, because the metal combustion promoting catalyst particles are larger, the contact area between the metal combustion promoting catalyst and the boron particles is reduced, the combustion rate promotion efficiency is low, the ignition temperature cannot be effectively reduced, and a large amount of metal combustion promoting catalyst needs to be added to solve the problems, so that the energy density of fuel is reduced. The invention adopts the droplet microfluidic technology to introduce the metal combustion promoting catalyst into the fuel microspheres, and realizes the low-loading and uniform distribution of the metal combustion promoting catalyst in the fuel microspheres by the adsorption of chitosan on 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 the chitosan to obtain a dispersed phase solution, dispersing span-80 into n-octanol to obtain a continuous phase solution, and dispersing glutaraldehyde into an n-octanol solution containing span-80 to obtain a receiving phase solution; s22, introducing the dispersed phase solution and the continuous phase solution prepared in the step S21 into a droplet microfluidic device at a certain flow rate to obtain a monodisperse droplet (the schematic diagram of the synthesis process of the monodisperse droplet is shown in figure 1); s23, the monodisperse liquid drops obtained in the step S22 are introduced into the receiving phase solution obtained in the step S21, and the fuel microspheres are obtained after reaction.
In some embodiments of the invention, the monodisperse droplet obtained in step S22 has 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 invention, in step S22, the dispersed phase solution is introduced into the droplet microfluidic device at a flow rate of 5 to 10 μ L/min; in the step S22, the continuous phase solution is introduced into the droplet microfluidic device at a flow rate of 10-100 μ L/min. Therefore, the particle size of the fuel microspheres can be effectively controlled by controlling the flow 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 is understood that the specific step of coating the chitosan on the surface of the boron particle in step 31 may include the following:
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 an n-octanol solution containing span-80 to obtain a receiving phase solution; the concentration of boron particles in the dispersed 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 dispersed 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 the flow rate of 10-100 mu L/min to obtain monodisperse droplets with the diameter of 18.5-108 mu m;
3) And (3) introducing the monodisperse liquid 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, there is provided a propellant comprising fuel microspheres as hereinbefore described.
It will be appreciated that the propellant may include conventional materials such as binders, curing agents, plasticizers, bonding agents, etc. in addition to the fuel microspheres described above, and will not be described in any greater detail herein.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Examples
Example 1
The preparation method of the fuel microsphere comprises the following steps:
(1) Preparation of the dispersed, continuous and receiver phases
Preparation of dispersed phase: 0.075g (0.75 wt%) of chitosan and 0.15g of acetic acid are added into 9.475g of deionized water and stirred to obtain a clear solution, 0.3g (3 wt%) of nano boron (nB, the particle size is 50-80 nm) is added into the solution, and then ultrasonic treatment is carried out for 3 hours to uniformly disperse the nano boron into a dispersed phase.
Preparation of continuous phase: 1.2g (2 wt%) of span-80 was added to 58.8g of n-octanol and stirred to obtain a clear solution to obtain a continuous phase.
Preparation of the receiving phase: adding 0.5wt% of saturated glutaraldehyde solution in n-octanol into 2wt% span-80 solution, and stirring to obtain clear solution, thus obtaining a receiving phase.
(2) Preparation of fuel microspheres
As shown in FIG. 1, the dispersed phase (Q) was injected using a single channel syringe pump d ) Injecting into a droplet microfluidic device at a flow rate of 5 μ L/min, and pumping the continuous phase (Q) with a dual-channel injection pump c ) Injecting the mixture into a droplet microfluidic device at a flow rate of 10 mu L/min, forming monodisperse droplets with uniform size under the continuous shearing of a continuous phase (the preparation process of the monodisperse droplets is shown in figure 2, and the particle size of the monodisperse droplets is shown in figure 3), continuously introducing the droplets into a receiving phase, stirring and solidifying for 12h, centrifuging, washing, and vacuum drying for 12h to obtain the monodisperse fuel microspheres.
Example 2:
the preparation method of the fuel microsphere is basically the same as that of example 1, except that the flow rate of the continuous phase is 20 μ L/min; the preparation process of the monodisperse droplets in the 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 preparation method of the fuel microsphere is basically the same as that of example 1, except that the flow rate of the continuous phase is 30 μ L/min; the process for preparing 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 preparation method of the fuel microsphere is basically the same as that of example 1, except that the flow rate of the continuous phase is 40 μ L/min; the process for preparing 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 preparation method of the fuel microsphere is basically the same as that of example 1, except that the flow rate of the continuous phase is 50 μ L/min; the process for preparing 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 microsphere is prepared by the same method as example 1, except that the flow rate of the dispersed phase is 7.5 μ L/min, the flow rate of the continuous phase is 15 μ L/min, and the particle size of the monodisperse droplet in this example is shown in FIG. 3.
Example 7:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 8:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 9:
the fuel microsphere is prepared in substantially the same manner as in example 6, except that the flow rate of the continuous phase is 60 μ L/min, and the particle size of the monodisperse droplet in this example is shown in fig. 3.
Example 10:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 11:
the fuel microsphere is prepared in the same manner as in example 1, except that the flow rate of the dispersed phase is 10. Mu.L/min, the flow rate of the continuous phase is 20. Mu.L/min, and the particle size of the monodisperse droplet in this example is shown in FIG. 3.
Example 12:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 13:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 14:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 15:
the fuel microsphere was prepared substantially 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 droplet in this example is shown in FIG. 3.
Example 16:
the preparation method of the fuel microsphere is basically the same as that of example 2, except that the content of nano boron in the dispersed phase is 2wt%, the SEM image of the fuel microsphere is shown in FIG. 4, and the particle size distribution of the fuel microsphere is shown in FIG. 6.
Example 17:
the preparation method of the fuel microsphere is basically the same as that of example 2, except that the content of nano boron in the dispersed phase is 4wt%, the SEM image of the fuel microsphere is shown in FIG. 4, and the particle size distribution of the fuel microsphere is shown in FIG. 6.
Example 18:
the preparation method of the fuel microsphere is basically the same as that of example 2, except that the content of nano boron in the dispersed phase is 5wt%, the SEM image of the fuel microsphere is shown in FIG. 4, and the particle size distribution of the fuel microsphere is shown in FIG. 6.
Example 19:
the fuel microsphere was prepared substantially as in example 17, except that 0.033g of molybdenum acetylacetonate as a combustion promoting catalyst was added to the dispersed phase, the optical image of the fuel microsphere is shown in FIG. 5, and the particle size distribution of the fuel microsphere is shown in FIG. 6.
Example 20:
the fuel microsphere was prepared substantially as in example 17, except that 0.033g of iron acetylacetonate as a combustion promoting catalyst was added to the dispersed phase, the optical image of the fuel microsphere is shown in FIG. 5, and the particle size distribution of the fuel microsphere is shown in FIG. 6.
Example 21:
the fuel microsphere was prepared substantially as in example 17, except that 0.033g of cobalt acetylacetonate as a combustion promoting catalyst was added to the dispersed phase, the optical image of the fuel microsphere is shown in FIG. 5, and the particle size distribution of the fuel microsphere is 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 figure 4.
And (3) testing the ignition temperature:
5mg of the fuel microspheres of examples 1 to 21 and the fuel of comparative example 1 were taken, respectively, and the thermal properties of the samples were measured at a temperature rise rate of 10 ℃/min in an air atmosphere using a TG-DSC comprehensive thermal analyzer at a temperature ranging from room temperature to 1000 ℃, and the ignition temperature was obtained by a tangent method, and is shown in Table 1.
Constant volume combustion and combustion heat value test:
0.15g of fuel (fuel comprising the fuel microspheres of examples 1-21 and the fuel of comparative example 1, respectively) was taken to test the combustion calorific value of the sample using an oxygen bomb calorimeter under an oxygen atmosphere of 3MPa while taking the pressure change during combustion. The heat of combustion and the maximum pressure peak for the fuel microspheres of examples 1-21 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 specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A fuel microsphere, comprising:
boron particles having a particle size of the order of nanometers;
chitosan, wherein the chitosan is coated on the surface of the boron particles.
2. The fuel microsphere of claim 1, further comprising:
a metal combustion promotion 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 acetylacetone metal salt 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.
3. The fuel microsphere of claim 1 or 2, wherein the diameter of the fuel microsphere is 10-40 μ ι η;
and/or, based on the total mass of the fuel microsphere, the content of the chitosan is 5-50wt%;
and/or the particle size of the boron particles is 50-80nm.
4. A method of producing the fuel microsphere of any one of claims 1 to 3, comprising:
and coating chitosan on the surface of the boron particles to obtain the fuel microspheres.
5. The method of claim 4, further comprising:
and adsorbing a metal combustion promotion catalyst on the surface of the chitosan to obtain the fuel microsphere.
6. The method of claim 4 or 5, wherein coating chitosan on the surface of the boron particle comprises:
s11, 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 an n-octanol solution containing span-80 to obtain a receiving phase solution;
s12, introducing the dispersed 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, the monodisperse liquid obtained in the step S12 is dripped into the receiving phase solution obtained in the step S11, and the fuel microsphere is obtained after reaction;
and/or the diameter of the monodisperse droplet obtained in step S12 is 18.5-108 μm.
7. The method according to claim 6, wherein 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%;
and/or in the step S12, the dispersion 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 the flow rate of 10-100 mu L/min.
8. The method of claim 5, wherein adsorbing a metal-based catalyst on the surface of the chitosan comprises:
s21, dispersing the boron particles and the metal combustion-promoting catalyst 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 an n-octanol solution containing span-80 to obtain a receiving phase solution;
s22, introducing the dispersed 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 liquid drops obtained in the step S22 into the receiving phase solution obtained in the step S21, and reacting to obtain the fuel microspheres;
and/or the diameter of the monodisperse droplet obtained in step S22 is 18.5-108 μm.
9. The method of claim 5, wherein adsorbing a metal-based 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, characterized by comprising the fuel microspheres according to any one of claims 1-3.
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Citations (3)
| 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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Patent Citations (3)
| 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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