CN114164371A - Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof - Google Patents
Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof Download PDFInfo
- Publication number
- CN114164371A CN114164371A CN202111486578.9A CN202111486578A CN114164371A CN 114164371 A CN114164371 A CN 114164371A CN 202111486578 A CN202111486578 A CN 202111486578A CN 114164371 A CN114164371 A CN 114164371A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- preparing
- mass
- nitrogen alloy
- porous particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
Abstract
The invention discloses an activator for preparing vanadium-nitrogen alloy and a preparation method thereof, and relates to the technical field of alloy materials. When the active agent for preparing the vanadium-nitrogen alloy is prepared, firstly, vanadium nitrate reacts with 2-amino terephthalic acid to prepare a metal organic framework, then terephthalic acid and melamine are polymerized on the metal organic framework to prepare conjugated porous particles, the conjugated porous particles react with carbon oxide nano tubes in sequence to carry out pre-reaction, then oxalic acid is adsorbed, and finally, the modified carbon nano tubes react to seal and compact the surface to prepare the vanadium-nitrogen alloy. The active agent for preparing the vanadium-nitrogen alloy has excellent use effect, and the effect is durable and easy to store.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to an activator for preparing vanadium-nitrogen alloy and a preparation method thereof.
Background
The vanadium-nitrogen alloy is a novel alloy additive, and can replace ferrovanadium to be used for producing microalloyed steel. The vanadium nitride added into the steel can improve the comprehensive mechanical properties of the steel, such as strength, toughness, ductility, thermal fatigue resistance and the like, and enables the steel to have good weldability. Under the condition of achieving the same strength, the vanadium nitride is added, so that the adding amount of vanadium is saved by 30-40%, and the cost is further reduced.
At present, various vanadium-nitrogen alloy production methods are reported in related aspects, and the methods are different in aspects such as raw material proportion, preparation process, heating furnace and kiln. Grinding aid is usually added in the grinding process to accelerate grinding and reduce energy consumption in the vanadium-nitrogen alloy preparation process, carbon powder coal powder is added in the calcining process to perform carbothermic reduction and heating, so that although the energy consumption can be effectively reduced and the vanadium-nitrogen alloy can be prepared in an accelerated manner, other impurities are easily generated in the adding process, and the production process is complicated.
Disclosure of Invention
The invention aims to provide an activator for preparing vanadium-nitrogen alloy and a preparation method thereof, which aim to solve the problems in the prior art.
The active agent for preparing the vanadium-nitrogen alloy is characterized by mainly comprising the following components in parts by weight: 15-17 parts of conjugated porous particles, 7-13 parts of carbon oxide nanotubes, 23-37 parts of modified carbon nanotubes and 38-52 parts of oxalic acid.
Preferably, the conjugated porous particles are prepared by reacting vanadium nitrate and 2-aminoterephthalic acid to prepare a metal-organic framework, and polymerizing melamine and terephthalic acid on the metal-organic framework.
Preferably, the carbon oxide nanotube is prepared by oxidizing the carbon nanotube with concentrated sulfuric acid, potassium permanganate and hydrogen peroxide in sequence.
Preferably, the modified carbon nanotube is prepared by reacting an oxidized carbon nanotube with monochloroacetic acid.
As optimization, the preparation method of the activating agent for preparing the vanadium-nitrogen alloy mainly comprises the following preparation steps:
(1) preparation of conjugated porous particles: terephthalic acid, a metal organic framework, dimethyl sulfoxide and pure water are mixed according to a mass ratio of 1: 1: 10: 10-1: 1: 15: 15, uniformly mixing, adding carbodiimide with the mass of 0.01-0.03 time of that of a metal organic framework, stirring and reacting for 30-40 min at the temperature of 20-30 ℃ at 1500-2000 r/min, then adding melamine with the mass of 2-4 times of that of the metal organic framework and terephthalic acid with the mass of 3-5 times of that of the metal organic framework, stirring and reacting for 3-5 h at the temperature of 20-30 ℃ at 1500-2000 r/min, washing for 3-5 times by using absolute ethyl alcohol after filtering, and drying for 6-8 h at-10-1 ℃ at 5-10 Pa to obtain conjugated porous particles;
(2) preparing the modified carbon nano tube: mixing the oxidized carbon nanotube and pure water according to the mass ratio of 1: 80-1: 100, uniformly mixing, adding sodium hydroxide with the mass being 20-30 times that of the oxidized carbon nanotube and monochloroacetic acid with the mass being 15-25 times that of the oxidized carbon nanotube, reacting for 3-4 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, filtering at 60-70 ℃, washing for 3-5 times by using pure water, and drying for 4-6 hours at the temperature of-10 to-5 ℃ and under the pressure of 5-10 Pa to prepare the modified carbon nanotube;
(3) preparation of the active agent: pre-reacting the conjugated porous particles, immersing the conjugated porous particles into a boiling oxalic acid solution 8-10 times of the mass of the conjugated porous particles, keeping the solution in a boiling state for 3-5 min, stirring at 400-600 r/min, cooling to 10-20 ℃ at a cooling speed of 5 ℃/min, filtering, drying at 60-70 ℃ for 4-6 h, and mixing with the modified carbon nano tube, wherein a sulfuric acid solution with the mass fraction of 70-90% is prepared by the following steps of: 0.8: 10-1: 1: 15, uniformly mixing, stirring at 80-90 ℃ for reaction for 3-5 h at 800-1000 r/min, filtering, sequentially washing with water and ethanol at 1-5 ℃ for 3-5 times respectively, and drying at 60-70 ℃ for 4-6 h to prepare the active agent for preparing the vanadium-nitrogen alloy.
As optimization, the preparation method of the metal organic framework in the step (1) comprises the following steps: mixing vanadium nitrate and pure water according to a mass ratio of 1: 10-1: 15, uniformly mixing, adding 2-amino terephthalic acid with the mass of 0.9-1.1 times that of vanadium nitrate, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05-0.08 times that of vanadium nitrate, stirring at 20-30 ℃ and 800-1000 r/min for 30-40 min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting at 200-250 ℃ for 7-9 h, cooling to 20-30 ℃, performing centrifugal separation, washing with N, N-dimethylformamide and absolute ethyl alcohol for 3-5 times respectively, soaking in the absolute ethyl alcohol at 60-70 ℃ for 20-24 h, cooling to 20-30 ℃, filtering, and drying at-10-1 ℃ and 5-10 Pa for 6-8 h to prepare the catalyst.
As an optimization, the preparation method of the oxidized carbon nanotube in the step (2) comprises the following steps: mixing a carbon nano tube with 98% concentrated sulfuric acid in a mass ratio of 1: 10-1: 15, uniformly mixing, adding potassium permanganate with the mass of 0.8-1.2 times that of the carbon nano tube, reacting for 4-6 hours at 50-60 ℃ under the condition of 30-40 kHz ultrasonic oscillation, controlling the temperature to be 1-5 ℃, adding hydrogen peroxide with the mass of 0.1-0.3 time that of the carbon nano tube, stirring for 10-15 minutes at the rotating speed of 800-1000 r/min, putting the mixture into a centrifugal machine, centrifugally separating at 6000-8000 r/min, washing separated sediments for 3-5 times by pure water, and drying for 4-6 hours at 60-70 ℃ to prepare the nano-tube.
As an optimization, the pre-reaction method in the step (3) comprises the following steps: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 70-90% in a mass ratio of 1: 0.5: 10-1: 0.8: 15, uniformly mixing, stirring and reacting at 80-90 ℃ for 3-5 h at 800-1000 r/min, filtering, sequentially washing with water and ethanol at 1-5 ℃ for 3-5 times respectively, and drying at 60-70 ℃ for 4-6 h.
Preferably, the boiling oxalic acid solution in the step (3) is prepared by heating and boiling pure water under standard atmospheric pressure, adding oxalic acid with the mass of 0.5 time of that of the pure water until the oxalic acid is completely dissolved, and keeping the temperature for later use.
Compared with the prior art, the invention has the following beneficial effects:
when the active agent for preparing the vanadium-nitrogen alloy is prepared, firstly, vanadium nitrate reacts with 2-amino terephthalic acid to prepare a metal organic framework, then terephthalic acid and melamine are polymerized on the metal organic framework to prepare conjugated porous particles, the conjugated porous particles react with carbon oxide nano tubes in sequence to carry out pre-reaction, then oxalic acid is adsorbed, and finally, the modified carbon nano tubes react to seal and compact the surface to prepare the vanadium-nitrogen alloy.
Firstly, the active agent for preparing the vanadium-nitrogen alloy prepared by the invention has good adsorption effect on organic matters by the internal conjugated porous particles, the adsorbed oxalic acid has high melting point, so that the adsorbed oxalic acid is stored in the conjugated porous particles in a solid form, the conjugated structure has higher stability and is easy to store, and meanwhile, hydroxyl on the oxidized carbon nano tube on the surface and carboxyl on the modified carbon nano tube are subjected to surface reaction and crosslinking, so that the density is high, the mechanical property of the material is further improved, the loss of internal substances is prevented, and the wear resistance and the lasting effectiveness of the material are improved.
Secondly, when the vanadium-nitrogen alloy is prepared for use, the conjugated porous particles and the surface formed by crosslinking the carbon oxide nanotube and the modified carbon nanotube are added in the initial grinding process, so that the mechanical property is good, the grinding process is promoted, and when the surface is worn, oxalic acid absorbed inside can be dissolved in the ground water and combined with active sites formed by the fracture of vanadium pentoxide particles, so that vanadium pentoxide is prevented from agglomerating and the grinding is accelerated; in the calcining process, the carbon oxide nanotube and the modified carbon nanotube which are worn and attached to the vanadium pentoxide and the oxalic acid combined on the vanadium pentoxide active site can be decomposed to form gas, so that the vanadium pentoxide is prevented from sintering, nitrogen is prevented from entering the interior of the vanadium pentoxide to be nitrided, meanwhile, the oxygen element in the vanadium pentoxide can be subjected to carbon thermal reduction, in addition, the conjugated porous particles contain melamine monomer which can be cracked to generate nitrogen, and the nitrogen is nitrided from the interior, so that the product purity is improved, and the oxygen content is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing each index of the activator for preparing vanadium-nitrogen alloy, which is prepared in the following examples, as follows:
the use effect is as follows: dispersing the same mass of the active agent for preparing the vanadium-nitrogen alloy obtained in each embodiment and a comparative example material in a pulverizer, adding vanadium pentoxide with the mass 1 time that of the active agent for preparing the vanadium-nitrogen alloy and distilled water with the mass 0.3 time that of the vanadium pentoxide, pulverizing at 10 ℃ until the particle diameter is less than 0.9mm to obtain vanadium pentoxide particles, placing the vanadium pentoxide particles in a nitriding furnace, inputting nitrogen to ensure that the air pressure in the furnace reaches 0.5MPa, sequentially calcining at 120 ℃ for 15min, calcining at 800 ℃ for 30min, calcining at 1100 ℃ for 4h, calcining at 1900 ℃ for 40min, cooling to 10 ℃, pulverizing until the particle diameter is less than 0.5mm to obtain the vanadium-nitrogen alloy, and measuring and recording the oxygen content by using a trace oxygen analyzer.
Durability: the same mass of the active agent for preparing the vanadium-nitrogen alloy obtained in each example and the comparative example material is taken, the active agent and the comparative example material are placed in an indoor environment with the same temperature, pressure and humidity for 30 days, the use effect experiment is carried out again to prepare the vanadium-nitrogen alloy, the oxygen content of the vanadium-nitrogen alloy after being placed for 30 days is measured and recorded by a trace oxygen analyzer, and the retention rate is calculated as (1-30 days oxygen content)/(1-initial oxygen content).
Example 1
An active agent for preparing vanadium-nitrogen alloy mainly comprises the following components in parts by weight: 14 parts of conjugated porous particles, 7 parts of oxidized carbon nanotubes, 23 parts of modified carbon nanotubes and 38 parts of oxalic acid.
The preparation method of the active agent for preparing the vanadium-nitrogen alloy mainly comprises the following preparation steps of:
(1) preparation of conjugated porous particles: mixing vanadium nitrate and pure water according to a mass ratio of 1: 10, uniformly mixing, adding 2-amino terephthalic acid with the mass of 0.9 time that of vanadium nitrate, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05 time that of vanadium nitrate, stirring for 40min at 20 ℃ and 800r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 9h at 200 ℃, cooling to 20 ℃, performing centrifugal separation, washing for 3 times by using N, N-dimethylformamide and absolute ethyl alcohol respectively, soaking in absolute ethyl alcohol at 60 ℃ for 24h, cooling to 20 ℃, filtering, drying for 8h at-10 ℃ and 5Pa to prepare a metal organic framework, mixing terephthalic acid, the metal organic framework, dimethyl sulfoxide and pure water according to the mass ratio of 1: 1: 10: 10, uniformly mixing, adding carbodiimide with the mass of 0.01 time of that of a metal organic framework, stirring and reacting for 40min at the temperature of 20 ℃ and 1500r/min, then adding melamine with the mass of 2 times of that of the metal organic framework and terephthalic acid with the mass of 3 times of that of the metal organic framework, stirring and reacting for 5h at the temperature of 20 ℃ and 1500r/min, washing for 3 times by using absolute ethyl alcohol after filtering, drying for 8h at the temperature of-10 ℃ and 5Pa to prepare conjugated porous particles, reacting vanadium nitrate and 2-aminoterephthalic acid to prepare the metal organic framework, performing dehydration condensation on amino on the metal organic framework and carboxyl on the terephthalic acid, performing dehydration condensation on the carboxyl on the terephthalic acid and the amino on the melamine to prepare the conjugated porous particles, and performing neutral and external conjugated polymerization on the metal organic framework to ensure that the conjugated porous particles have complex pore structures, the vanadium-nitrogen alloy has good adsorption capacity, can be used as a carrier of subsequent oxalic acid, and the conjugated structure can improve the mechanical property of the product, so that the product has better grinding-aid effect when the vanadium-nitrogen alloy is prepared;
(2) preparing the modified carbon nano tube: mixing a carbon nano tube with 98% concentrated sulfuric acid in a mass ratio of 1: 10, uniformly mixing, adding potassium permanganate with the mass of 0.8 time that of the carbon nano tube, reacting for 6 hours under the conditions of 50 ℃ and 30kHz ultrasonic oscillation, controlling the temperature to be 1 ℃, adding hydrogen peroxide with the mass of 0.1 time that of the carbon nano tube, stirring for 15 minutes at the rotating speed of 800r/min, putting the mixture into a centrifugal machine, centrifugally separating at 6000r/min, washing separated sediments for 3 times by using pure water, drying for 6 hours at the temperature of 60 ℃ to prepare the carbon oxide nano tube, and mixing the carbon oxide nano tube and the pure water according to the mass ratio of 1: 80, adding sodium hydroxide which is 20 times of the mass of the carbon oxide nano tube and monochloroacetic acid which is 15 times of the mass of the carbon oxide nano tube, reacting at 50 deg.C and 30kHz under ultrasonic oscillation for 4 hr, filtering at 60 deg.C, washing with pure water for 3 times, drying for 6h at the temperature of minus 10 ℃ and under the pressure of 5Pa to prepare a modified carbon nano tube, oxidizing the carbon nano tube by concentrated sulfuric acid, potassium permanganate and hydrogen peroxide to prepare a carbon oxide nano tube, introducing oxygen-containing groups such as hydroxyl, epoxy, carbonyl, aldehyde group and the like, reacting with monochloroacetic acid to prepare a carboxyl group, preparing the modified carbon nano tube, enabling the groups on the modified carbon nano tube to be combined on vanadium powder in a grinding-assisted manner when preparing vanadium-nitrogen alloy, accelerating grinding, the vanadium powder can also be used as a good reducing agent to remove oxygen in the vanadium powder during calcination, and can simultaneously intersect and play a role in sealing the conjugated porous particles;
(3) preparation of the active agent: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 70% according to the mass ratio of 1: 0.5: 10, uniformly mixing, stirring and reacting at 80 ℃ for 5h at 800r/min, filtering, washing with 1 ℃ water and ethanol for 3 times respectively, drying at 60 ℃ for 6h, immersing in boiling oxalic acid solution with the mass 8 times that of the conjugated porous particles, heating and keeping boiling the pure water under standard atmospheric pressure, adding oxalic acid with the mass 0.5 time that of the pure water until the oxalic acid is completely dissolved, keeping the solution in the boiling state for 3min, stirring at 400r/min, cooling to 10 ℃ at the cooling speed of 5 ℃/min, filtering, drying at 60 ℃ for 6h, mixing with the modified carbon nano tube, and mixing 70 mass percent sulfuric acid solution according to the mass ratio of 1: 0.8: 10, mixing uniformly, stirring and reacting at 80 ℃ at 800r/min for 5h, filtering, washing with water and ethanol at 1 ℃ for 3 times respectively in sequence, drying at 60 ℃ for 6h to prepare the active agent for preparing the vanadium-nitrogen alloy, pre-reacting the conjugated porous particles with the carbon oxide nano tubes, dehydrating and grafting hydroxyl groups, epoxy groups and carboxyl groups on the conjugated porous particles, adsorbing oxalic acid inside, finally modifying the carboxyl groups on the carbon nano tubes, dehydrating and cross-linking the hydroxyl groups and the epoxy groups on the pre-reacted conjugated porous particles to seal the surfaces to prepare the product, wherein the oxalic acid sealed in the active agent for preparing the vanadium-nitrogen alloy is solid at normal temperature and has good preservation effect when sealed in the conjugated porous particles, meanwhile, the oxalic acid has small molecular weight, can be more carefully combined on the vanadium powder, and further improves the grinding aiding effect and the subsequent calcining effect.
Example 2
An active agent for preparing vanadium-nitrogen alloy mainly comprises the following components in parts by weight: 15 parts of conjugated porous particles, 9 parts of carbon oxide nanotubes, 30 parts of modified carbon nanotubes and 45 parts of oxalic acid.
The preparation method of the active agent for preparing the vanadium-nitrogen alloy mainly comprises the following preparation steps of:
(1) preparation of conjugated porous particles: mixing vanadium nitrate and pure water according to a mass ratio of 1: 12, uniformly mixing, adding 2-amino terephthalic acid with the mass 1 time that of vanadium nitrate, adding hydrofluoric acid with the mass fraction 40% that of vanadium nitrate with the mass 0.06 time that of vanadium nitrate, stirring for 35min at 25 ℃ and 900r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 8h at 230 ℃, cooling to 25 ℃, performing centrifugal separation, washing for 4 times with N, N-dimethylformamide and absolute ethyl alcohol respectively, soaking again in absolute ethyl alcohol with the temperature of 65 ℃ for 22h, cooling to 25 ℃, filtering, drying for 7h at-5 ℃ and 8Pa to prepare a metal organic framework, mixing terephthalic acid, the metal organic framework, dimethyl sulfoxide and pure water according to the mass ratio of 1: 1: 12: 12, uniformly mixing, adding carbodiimide with the mass of 0.02 time of that of the metal organic framework, stirring and reacting for 35min at 25 ℃ and 1800r/min, then adding melamine with the mass of 3 times of that of the metal organic framework and terephthalic acid with the mass of 4 times of that of the metal organic framework, stirring and reacting for 4h at 25 ℃ and 1800r/min, washing for 4 times by using absolute ethyl alcohol after filtering, and drying for 7h at-5 ℃ and 8Pa to prepare the conjugated porous particles;
(2) preparing the modified carbon nano tube: mixing a carbon nano tube with 98% concentrated sulfuric acid in a mass ratio of 1: 12, uniformly mixing, adding potassium permanganate with the mass of 1 time that of the carbon nano tube, reacting for 5 hours under the conditions of 55 ℃ and 35kHz ultrasonic oscillation, controlling the temperature to be 3 ℃, adding hydrogen peroxide with the mass of 0.2 time that of the carbon nano tube, stirring for 12 minutes at the rotating speed of 900r/min, putting the mixture into a centrifugal machine, centrifugally separating at 7000r/min, washing separated sediments for 4 times by using pure water, drying for 5 hours at the temperature of 65 ℃ to prepare the carbon oxide nano tube, and mixing the carbon oxide nano tube and the pure water according to the mass ratio of 1: 90, adding sodium hydroxide with the mass of 25 times that of the carbon oxide nano tube and monochloroacetic acid with the mass of 20 times that of the carbon oxide nano tube, reacting for 3 hours at 55 ℃ and under the condition of 35kHz ultrasonic oscillation, filtering at 65 ℃, washing for 4 times by pure water, and drying for 5 hours at the temperature of minus 8 ℃ and under the pressure of 8Pa to obtain the modified carbon nano tube;
(3) preparation of the active agent: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 80% in a mass ratio of 1: 0.6: 12, uniformly mixing, stirring and reacting at 85 ℃ for 4h at 900r/min, filtering, washing with 3 ℃ water and ethanol for 4 times respectively, drying at 65 ℃ for 3h, immersing in boiling oxalic acid solution with the mass 9 times that of the conjugated porous particles, heating and keeping boiling the pure water under standard atmospheric pressure, adding oxalic acid with the mass 0.5 time that of the pure water until the oxalic acid is completely dissolved, keeping the solution in the boiling state for 4min, stirring at 500r/min, cooling to 15 ℃ at the cooling speed of 5 ℃/min, filtering, drying at 65 ℃ for 5h, mixing with the modified carbon nano tube, and mixing 80 mass percent sulfuric acid solution according to the mass ratio of 1: 0.9: 12, uniformly mixing, stirring at 85 ℃ and 900r/min for reaction for 4h, filtering, sequentially washing with water and ethanol at 3 ℃ for 4 times respectively, and drying at 65 ℃ for 5h to prepare the activating agent for preparing the vanadium-nitrogen alloy.
Example 3
An active agent for preparing vanadium-nitrogen alloy mainly comprises the following components in parts by weight: 17 parts of conjugated porous particles, 13 parts of oxidized carbon nanotubes, 37 parts of modified carbon nanotubes and 52 parts of oxalic acid.
The preparation method of the active agent for preparing the vanadium-nitrogen alloy mainly comprises the following preparation steps of:
(1) preparation of conjugated porous particles: mixing vanadium nitrate and pure water according to a mass ratio of 1: 15, uniformly mixing, adding 2-amino terephthalic acid with the mass of 1.1 times that of vanadium nitrate, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.08 times that of vanadium nitrate, stirring for 30min at 30 ℃ and 1000r/min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting for 7h at 250 ℃, cooling to 30 ℃, performing centrifugal separation, washing for 5 times by using N, N-dimethylformamide and absolute ethyl alcohol respectively, soaking in absolute ethyl alcohol at 70 ℃ for 20h, cooling to 30 ℃, filtering, drying for 6h at-1 ℃ and 10Pa to prepare a metal organic framework, mixing terephthalic acid, the metal organic framework, dimethyl sulfoxide and pure water according to the mass ratio of 1: 1: 15: 15, uniformly mixing, adding carbodiimide with the mass of 0.03 time of that of the metal organic framework, stirring and reacting for 40min at 30 ℃ at 2000r/min, then adding melamine with the mass of 4 times of that of the metal organic framework and terephthalic acid with the mass of 5 times of that of the metal organic framework, stirring and reacting for 3h at 30 ℃ at 2000r/min, washing for 5 times by using absolute ethyl alcohol after filtering, and drying for 6h at-1 ℃ and 10Pa to prepare the conjugated porous particles;
(2) preparing the modified carbon nano tube: mixing a carbon nano tube with 98% concentrated sulfuric acid in a mass ratio of 1: 15, uniformly mixing, adding potassium permanganate with the mass of 1.2 times that of the carbon nano tube, reacting for 4 hours under the conditions of 60 ℃ and 40kHz ultrasonic oscillation, controlling the temperature to be 5 ℃, adding hydrogen peroxide with the mass of 0.3 time that of the carbon nano tube, stirring for 10 minutes at the rotating speed of 1000r/min, putting the mixture into a centrifugal machine, centrifugally separating at 8000r/min, washing separated sediments for 5 times by using pure water, drying for 4 hours at 70 ℃ to prepare the carbon oxide nano tube, and mixing the carbon oxide nano tube and the pure water according to the mass ratio of 1: 100, adding sodium hydroxide with the mass 30 times that of the carbon oxide nano tube and monochloroacetic acid with the mass 25 times that of the carbon oxide nano tube, reacting for 3 hours at 60 ℃ under the condition of 40kHz ultrasonic oscillation, filtering at 70 ℃, washing for 5 times by pure water, and drying for 4 hours at the temperature of minus 5 ℃ and under the pressure of 10Pa to obtain the modified carbon nano tube;
(3) preparation of the active agent: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 90% according to the mass ratio of 1: 0.8: 15, uniformly mixing, stirring and reacting at 90 ℃ for 3h at 1000r/min, filtering, washing with 5 ℃ water and ethanol for 5 times respectively, drying at 70 ℃ for 4h, immersing in boiling oxalic acid solution which is 10 times of the mass of the conjugated porous particles, heating and keeping boiling the pure water under standard atmospheric pressure, adding oxalic acid which is 0.5 times of the mass of the pure water until the oxalic acid is completely dissolved, keeping the solution in the boiling state for 3min, stirring at 600r/min, cooling to 20 ℃ at a cooling speed of 5 ℃/min, filtering, drying at 70 ℃ for 4h, mixing with the modified carbon nanotube, and mixing 90 mass percent sulfuric acid solution according to a mass ratio of 1: 1: 15, uniformly mixing, stirring at 90 ℃ for reaction for 3h at 1000r/min, filtering, sequentially washing with water and ethanol at 5 ℃ for 5 times respectively, and drying at 70 ℃ for 4h to prepare the activating agent for preparing the vanadium-nitrogen alloy.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 2. The active agent for preparing vanadium-nitrogen alloy is different from the active agent for preparing vanadium-nitrogen alloy in composition, wherein 'oxalic acid' is replaced by 'acetic acid'.
Comparative example 2
An active agent for preparing vanadium-nitrogen alloy mainly comprises the following components in parts by weight: 15 parts of conjugated porous particles, 39 parts of modified carbon nanotubes and 45 parts of oxalic acid.
The difference between the activating agent for preparing vanadium-nitrogen alloy and the activating agent in the embodiment 2 is only that the step (3) is different, and the step (3) is modified as follows: (3) preparation of the active agent: mixing the conjugated porous particles, the modified carbon nano tubes and a sulfuric acid solution with the mass fraction of 80% according to the mass ratio of 1: 0.6: 12, uniformly mixing, stirring and reacting at 85 ℃ for 4h at 900r/min, filtering, washing with 3 ℃ water and ethanol for 4 times respectively, drying at 65 ℃ for 3h, immersing in boiling oxalic acid solution with the mass 9 times that of the conjugated porous particles, heating and keeping boiling the pure water under standard atmospheric pressure, adding oxalic acid with the mass 0.5 time that of the pure water until the oxalic acid is completely dissolved, keeping the solution in the boiling state for 4min, stirring at 500r/min, cooling to 15 ℃ at the cooling speed of 5 ℃/min, filtering, drying at 65 ℃ for 5h, mixing with the modified carbon nano tube, and mixing 80 mass percent sulfuric acid solution according to the mass ratio of 1: 0.9: 12, uniformly mixing, stirring at 85 ℃ and 900r/min for reaction for 4h, filtering, sequentially washing with water and ethanol at 3 ℃ for 4 times respectively, and drying at 65 ℃ for 5h to prepare the activating agent for preparing the vanadium-nitrogen alloy.
Comparative example 3
An active agent for preparing vanadium-nitrogen alloy mainly comprises the following components in parts by weight: 15 parts of conjugated porous particles, 39 parts of carbon oxide nanotubes and 45 parts of oxalic acid.
The difference between the activating agent for preparing vanadium-nitrogen alloy and the activating agent in the embodiment 2 is only that the step (3) is different, and the step (3) is modified as follows: (3) preparation of the active agent: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 80% in a mass ratio of 1: 0.6: 12, uniformly mixing, stirring at 85 ℃ for reaction for 4h at 900r/min, filtering, washing with 3 ℃ water and ethanol for 4 times respectively, drying at 65 ℃ for 3h, immersing in boiling oxalic acid solution with the mass 9 times that of the conjugated porous particles, heating and boiling the pure water under standard atmospheric pressure, adding 0.5 time of oxalic acid with the mass of the pure water until the oxalic acid is completely dissolved, keeping the solution in the boiling state for 4min, stirring at 500r/min, and reducing the temperature by 5 ℃/min
| Oxygen content | Retention rate | Oxygen content | Retention rate | ||
| Example 1 | 0.2％ | 99.1％ | Comparative example 1 | 0.3％ | 88.3％ |
| Example 2 | 0.1％ | 99.2％ | Comparative example 2 | 0.2％ | 93.5％ |
| Example 3 | 0.1％ | 99.0％ | Comparative example 3 | 1.2％ | 98.9％ |
Cooling to 15 ℃, filtering, drying at 65 ℃ for 5 hours, mixing with the oxidized carbon nanotube and a sulfuric acid solution with the mass fraction of 80% according to the mass ratio of 1: 0.9: 12, uniformly mixing, stirring at 85 ℃ and 900r/min for reaction for 4h, filtering, sequentially washing with water and ethanol at 3 ℃ for 4 times respectively, and drying at 65 ℃ for 5h to prepare the activating agent for preparing the vanadium-nitrogen alloy.
Examples of effects
The following table 1 shows the results of performance analysis of the effects and durability of use using examples 1 to 3 of the present invention and comparative examples 1 to 3.
TABLE 1
As can be seen from the comparison of the experimental data of examples 1, 2 and 3 and comparative example 1 in table 1, the retention rates of examples 1, 2 and 3 and comparative example 1 are high, which indicates that compared with acetic acid, oxalic acid is not easy to form gas loss in the daily storage process, and meanwhile, oxalic acid is solid at normal temperature, so that the durability of the active agent for preparing vanadium-nitrogen alloy is improved; compared with the experimental data of examples 1, 2 and 3 and comparative example 2, the experimental data of examples 1, 2 and 3 shows that the retention rate of examples 1, 2 and 3 is higher than that of comparative example 2, which shows that compared with the prior art that the carbon oxide nanotubes are used for pre-reaction and then react with the modified carbon nanotubes, hydroxyl on the carbon oxide nanotubes and carboxyl on the modified carbon nanotubes can react to form a compact cross-linked surface, so that internal substances are not easy to run off, and the durability of the active agent for preparing the vanadium-nitrogen alloy is improved; the experimental data comparison of examples 1, 2 and 3 and comparative example 3 shows that the oxygen content of examples 1, 2 and 3 and comparative example 3 is low, which indicates that the pre-reaction of the carbon oxide nanotubes in the preparation of the active agent can be effectively combined on the conjugated porous particles compared with the modified carbon nanotubes, and simultaneously avoids the condition that the modified carbon nanotubes are crosslinked to block and shield the pore channels, so that more oxalic acid can be adsorbed and deposited in the adsorption process, and the use effect of the active agent for preparing the vanadium-nitrogen alloy is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The active agent for preparing the vanadium-nitrogen alloy is characterized by mainly comprising the following components in parts by weight: 15-17 parts of conjugated porous particles, 7-13 parts of carbon oxide nanotubes, 23-37 parts of modified carbon nanotubes and 38-52 parts of oxalic acid.
2. The activator for preparing vanadium-nitrogen alloy according to claim 1, wherein the conjugated porous particles are prepared by reacting vanadium nitrate and 2-aminoterephthalic acid to prepare a metal-organic framework, and polymerizing melamine and terephthalic acid on the metal-organic framework.
3. The activator for preparing vanadium-nitrogen alloy according to claim 2, wherein the oxidized carbon nanotube is prepared by oxidizing carbon nanotube with concentrated sulfuric acid, potassium permanganate and hydrogen peroxide in sequence.
4. The active agent for preparing vanadium-nitrogen alloy according to claim 3, wherein the modified carbon nanotubes are prepared by reacting carbon nanotubes with monochloroacetic acid.
5. The preparation method of the activating agent for preparing the vanadium-nitrogen alloy is characterized by mainly comprising the following preparation steps of:
(1) preparation of conjugated porous particles: terephthalic acid, a metal organic framework, dimethyl sulfoxide and pure water are mixed according to a mass ratio of 1: 1: 10: 10-1: 1: 15: 15, uniformly mixing, adding carbodiimide with the mass of 0.01-0.03 time of that of a metal organic framework, stirring and reacting for 30-40 min at the temperature of 20-30 ℃ at 1500-2000 r/min, then adding melamine with the mass of 2-4 times of that of the metal organic framework and terephthalic acid with the mass of 3-5 times of that of the metal organic framework, stirring and reacting for 3-5 h at the temperature of 20-30 ℃ at 1500-2000 r/min, washing for 3-5 times by using absolute ethyl alcohol after filtering, and drying for 6-8 h at-10-1 ℃ at 5-10 Pa to obtain conjugated porous particles;
(2) preparing the modified carbon nano tube: mixing the oxidized carbon nanotube and pure water according to the mass ratio of 1: 80-1: 100, uniformly mixing, adding sodium hydroxide with the mass being 20-30 times that of the oxidized carbon nanotube and monochloroacetic acid with the mass being 15-25 times that of the oxidized carbon nanotube, reacting for 3-4 hours under the condition of ultrasonic oscillation at 50-60 ℃ and 30-40 kHz, filtering at 60-70 ℃, washing for 3-5 times by using pure water, and drying for 4-6 hours at the temperature of-10 to-5 ℃ and under the pressure of 5-10 Pa to prepare the modified carbon nanotube;
(3) preparation of the active agent: pre-reacting the conjugated porous particles, immersing the conjugated porous particles into a boiling oxalic acid solution 8-10 times of the mass of the conjugated porous particles, keeping the solution in a boiling state for 3-5 min, stirring at 400-600 r/min, cooling to 10-20 ℃ at a cooling speed of 5 ℃/min, filtering, drying at 60-70 ℃ for 4-6 h, and mixing with the modified carbon nano tube, wherein a sulfuric acid solution with the mass fraction of 70-90% is prepared by the following steps of: 0.8: 10-1: 1: 15, uniformly mixing, stirring at 80-90 ℃ for reaction for 3-5 h at 800-1000 r/min, filtering, sequentially washing with water and ethanol at 1-5 ℃ for 3-5 times respectively, and drying at 60-70 ℃ for 4-6 h to prepare the active agent for preparing the vanadium-nitrogen alloy.
6. The method for preparing the active agent for preparing the vanadium-nitrogen alloy according to claim 5, wherein the method for preparing the metal-organic framework in the step (1) comprises the following steps: mixing vanadium nitrate and pure water according to a mass ratio of 1: 10-1: 15, uniformly mixing, adding 2-amino terephthalic acid with the mass of 0.9-1.1 times that of vanadium nitrate, adding hydrofluoric acid with the mass fraction of 40% with the mass of 0.05-0.08 times that of vanadium nitrate, stirring at 20-30 ℃ and 800-1000 r/min for 30-40 min, transferring to a reaction kettle with a polytetrafluoroethylene substrate, reacting at 200-250 ℃ for 7-9 h, cooling to 20-30 ℃, performing centrifugal separation, washing with N, N-dimethylformamide and absolute ethyl alcohol for 3-5 times respectively, soaking in the absolute ethyl alcohol at 60-70 ℃ for 20-24 h, cooling to 20-30 ℃, filtering, and drying at-10-1 ℃ and 5-10 Pa for 6-8 h to prepare the catalyst.
7. The method for preparing the active agent for preparing vanadium-nitrogen alloy according to claim 6, wherein the method for preparing the oxidized carbon nanotube in the step (2) comprises the following steps: mixing a carbon nano tube with 98% concentrated sulfuric acid in a mass ratio of 1: 10-1: 15, uniformly mixing, adding potassium permanganate with the mass of 0.8-1.2 times that of the carbon nano tube, reacting for 4-6 hours at 50-60 ℃ under the condition of 30-40 kHz ultrasonic oscillation, controlling the temperature to be 1-5 ℃, adding hydrogen peroxide with the mass of 0.1-0.3 time that of the carbon nano tube, stirring for 10-15 minutes at the rotating speed of 800-1000 r/min, putting the mixture into a centrifugal machine, centrifugally separating at 6000-8000 r/min, washing separated sediments for 3-5 times by pure water, and drying for 4-6 hours at 60-70 ℃ to prepare the nano-tube.
8. The method for preparing the active agent for preparing the vanadium-nitrogen alloy according to claim 7, wherein the pre-reaction in the step (3) is as follows: mixing the conjugated porous particles, the carbon oxide nanotubes and a sulfuric acid solution with the mass fraction of 70-90% in a mass ratio of 1: 0.5: 10-1: 0.8: 15, uniformly mixing, stirring and reacting at 80-90 ℃ for 3-5 h at 800-1000 r/min, filtering, sequentially washing with water and ethanol at 1-5 ℃ for 3-5 times respectively, and drying at 60-70 ℃ for 4-6 h.
9. The method for preparing the active agent for preparing the vanadium-nitrogen alloy as claimed in claim 8, wherein the boiling oxalic acid solution in the step (3) is prepared by heating and boiling pure water under standard atmospheric pressure, adding oxalic acid with the mass 0.5 times that of the pure water until the oxalic acid is completely dissolved, and keeping the temperature for standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111486578.9A CN114164371B (en) | 2021-12-07 | 2021-12-07 | Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111486578.9A CN114164371B (en) | 2021-12-07 | 2021-12-07 | Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114164371A true CN114164371A (en) | 2022-03-11 |
| CN114164371B CN114164371B (en) | 2022-07-01 |
Family
ID=80484027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111486578.9A Active CN114164371B (en) | 2021-12-07 | 2021-12-07 | Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114164371B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120021486A1 (en) * | 2009-01-16 | 2012-01-26 | Cerasela Zoica Dinu | Enzyme-based nanoscale decontaminating composites |
| CN104562177A (en) * | 2015-02-10 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of vanadium pentoxide/tungsten oxide co-deposited cubic crystals |
| CN106048284A (en) * | 2016-06-13 | 2016-10-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium-nitrogen alloy and preparation method thereof |
| JP2017193647A (en) * | 2016-04-21 | 2017-10-26 | コニカミノルタ株式会社 | Vanadium dioxide-containing particle and method for producing the same |
| CN107394207A (en) * | 2017-06-27 | 2017-11-24 | 宁波墨西科技有限公司 | A kind of graphene composite conductive powder and preparation method thereof |
| CN109136612A (en) * | 2018-09-25 | 2019-01-04 | 山东济钢合金材料科技有限公司 | A kind of preparation method of VN alloy |
| CN109280798A (en) * | 2018-11-28 | 2019-01-29 | 湖南众鑫新材料科技股份有限公司 | A kind of preparation method of hypoxemia VN alloy |
| CN110184521A (en) * | 2019-06-17 | 2019-08-30 | 承德燕北冶金材料有限公司 | A kind of compound density agent and the method that VN alloy is prepared using it |
| CN111020106A (en) * | 2019-12-13 | 2020-04-17 | 湖南众鑫新材料科技股份有限公司 | Vanadium-nitrogen alloy additive and preparation method thereof |
| CN112239629A (en) * | 2020-09-24 | 2021-01-19 | 桐城市儒和建材有限公司 | Alkali-resistant mildew-proof water-based black paint and preparation method thereof |
| CN113337750A (en) * | 2021-06-02 | 2021-09-03 | 承德燕北冶金材料有限公司 | Preparation method of vanadium-nitrogen alloy |
-
2021
- 2021-12-07 CN CN202111486578.9A patent/CN114164371B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120021486A1 (en) * | 2009-01-16 | 2012-01-26 | Cerasela Zoica Dinu | Enzyme-based nanoscale decontaminating composites |
| CN104562177A (en) * | 2015-02-10 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of vanadium pentoxide/tungsten oxide co-deposited cubic crystals |
| JP2017193647A (en) * | 2016-04-21 | 2017-10-26 | コニカミノルタ株式会社 | Vanadium dioxide-containing particle and method for producing the same |
| CN106048284A (en) * | 2016-06-13 | 2016-10-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium-nitrogen alloy and preparation method thereof |
| CN107394207A (en) * | 2017-06-27 | 2017-11-24 | 宁波墨西科技有限公司 | A kind of graphene composite conductive powder and preparation method thereof |
| CN109136612A (en) * | 2018-09-25 | 2019-01-04 | 山东济钢合金材料科技有限公司 | A kind of preparation method of VN alloy |
| CN109280798A (en) * | 2018-11-28 | 2019-01-29 | 湖南众鑫新材料科技股份有限公司 | A kind of preparation method of hypoxemia VN alloy |
| CN110184521A (en) * | 2019-06-17 | 2019-08-30 | 承德燕北冶金材料有限公司 | A kind of compound density agent and the method that VN alloy is prepared using it |
| CN111020106A (en) * | 2019-12-13 | 2020-04-17 | 湖南众鑫新材料科技股份有限公司 | Vanadium-nitrogen alloy additive and preparation method thereof |
| CN112239629A (en) * | 2020-09-24 | 2021-01-19 | 桐城市儒和建材有限公司 | Alkali-resistant mildew-proof water-based black paint and preparation method thereof |
| CN113337750A (en) * | 2021-06-02 | 2021-09-03 | 承德燕北冶金材料有限公司 | Preparation method of vanadium-nitrogen alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114164371B (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017181826A1 (en) | Method for manufacturing three-dimensional hierarchical porous graphene powder | |
| CN110773156B (en) | Transition metal monatomic catalyst, preparation method and application thereof | |
| CN107096394B (en) | High-permeability graphene-doped proton conductor dense ceramic hydrogen permeation membrane and preparation method thereof | |
| CN111617645A (en) | Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material | |
| CN111821980A (en) | Catalyst for morpholine production and preparation method thereof | |
| CN114164371B (en) | Activating agent for preparing vanadium-nitrogen alloy and preparation method thereof | |
| CN112516787B (en) | Indoor formaldehyde purification material and preparation method thereof | |
| CN112479207A (en) | Method for recycling activated carbon, double-electric-layer capacitor comprising activated carbon recycled by method and preparation method of double-electric-layer capacitor | |
| CN112875700A (en) | Preparation of asphalt-based carbon microspheres and application of asphalt-based carbon microspheres in supercapacitor electrodes | |
| CN108499534B (en) | Compact gas separation hybrid material containing graphene metal organic framework and preparation method thereof | |
| TWI519472B (en) | Silicon carbide powder (a) | |
| CN111808441B (en) | Precipitation method white carbon black surface modification method | |
| CN114899463A (en) | Organic-inorganic composite medium-temperature proton exchange membrane and preparation method thereof | |
| CN114292443A (en) | Coating treating agent capable of improving weather resistance of titanium dioxide and preparation method thereof | |
| CN108636440B (en) | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof | |
| CN114425367A (en) | Catalyst system for preparing acrylate through acetylene carbonylation, preparation and application thereof | |
| CN114558559B (en) | Carbon sphere-oxide composite catalytic material and preparation method and application thereof | |
| CN115961153A (en) | Method for recycling gas medium in vanadium-nitrogen alloy preparation process | |
| CN117299096B (en) | Iron oxyhydroxide desulfurizing agent based on resin substrate and preparation method thereof | |
| CN111940721B (en) | Method for loading nano metal oxide or nano metal material on porous carbon | |
| CN116832785B (en) | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof | |
| CN111732991A (en) | Composite oxygen carrier composition for chemical looping combustion and preparation method thereof | |
| JPH059812A (en) | Porous carbon fiber, its production, production of porous graphite fiber and treatment of porous carbon fiber | |
| CN115724813A (en) | Method for preparing 2, 5-furandicarboxylic acid | |
| CN114272907A (en) | Magnetic lignocellulose nano-microsphere and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |