CN107226472A - A kind of situ-combustion synthesis prepares B4The method of C nano pipe - Google Patents
A kind of situ-combustion synthesis prepares B4The method of C nano pipe Download PDFInfo
- Publication number
- CN107226472A CN107226472A CN201710324507.6A CN201710324507A CN107226472A CN 107226472 A CN107226472 A CN 107226472A CN 201710324507 A CN201710324507 A CN 201710324507A CN 107226472 A CN107226472 A CN 107226472A
- Authority
- CN
- China
- Prior art keywords
- self
- nano pipe
- situ
- prepares
- reaction
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/10—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium chloride with water vapour
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, belongs to ceramic nano Manifold technology field.This method is put into progress mechanical activation processing in high energy ball mill by that will mix boron oxide and magnesium powder in molar ratio；It is well mixed in molar ratio with CNT again, it is put into mould, block blank is pressed into 10~60MPa, it is placed in trigger in self-propagating reaction stove and carries out self-propagating reaction, product is immersed in watery hydrochloric acid, Strengthen education in closed reactor is placed in, last spray-wall interaction obtains high-purity boron carbide nanotube product.This method prepares the good two-dimentional ceramic nano pipe of high-purity, high activity, pyroelectricity.Cost of material is low, and energy consumption is low, simple to operate, requires low to process conditions and instrument and equipment, is that industrialized production is laid a good foundation.Activated using high-energy ball milling, improve raw material availability and product purity；Using self- propagating powder-making technique, the product of gained has purity high, and size distribution is controllable, the high advantage of powder activity.
Description
Technical field
The invention belongs to ceramic nano Manifold technology field, and in particular to a kind of situ-combustion synthesis prepares B4C nano pipe
Method.
Background technology
Boron carbide is mainly used in making boron carbide ceramics, and boron carbide ceramics has that density is small, hardness is high, high-modulus, strong resistance to
The features such as mill property, high antioxidant, stronger acid-resistant corrosion and excellent neutron-absorbing performance, before wide application
Scape, is widely used in bullet resistant material, wear-resisting and self-lubricating material, cutting and grinding instrument, radiation proof material and atomic pile control
System and shielding material etc..
Nano-tube material except as nano material it is a kind of have special quantum effect, surface and interface effect in addition to,
The thermoelectric properties such as electric conductivity, thermal conductivity and the superconductivity not possessed with nano-powder also.
This technique is with the new technology route system of mechanical activation, self-propagating synthesis, closed Strengthen education and acid solution pyrolysis cyclical
Take boron carbide nanotube, have the advantages that technological process it is short, without intermediate step, cost be low, good product performance, therefore be more easy to realize
Serialization, is one of most potential boron carbide nanotube preparation technology, meets the reduction cost of raw material, saves the energy
National economic development strategy, the industrialized economy benefit and social benefit of this technology is all very considerable.
The content of the invention
B is prepared it is an object of the invention to provide a kind of situ-combustion synthesis4The method of C nano pipe, by mechanical activation, certainly
Spread synthesis, closed Strengthen education and spray-wall interaction and obtain high-purity boron carbide nanotube product.This method be a kind of high-purity,
The preparation method of the good two-dimentional ceramic nano tube material of high activity, pyroelectricity.Cost of material of the present invention is low, and energy consumption is low, operation
Simply, low are required to process conditions and instrument and equipment, is that industrialized production is laid a good foundation.Activated, improved using high-energy ball milling
Raw material availability and product purity；Using self- propagating powder-making technique, the product of gained has purity high, and size distribution is controllable, powder
The advantages of end is active high.
A kind of situ-combustion synthesis of the present invention prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：(2~4)；
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 10~60MPa
Block blank is pressed into, is placed in self-propagating reaction stove and triggers progress self-propagating reaction, reaction mass, reaction mass cooling is obtained
Afterwards, nanotube-shaped B is obtained4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：(2~4)：(0.5~0.6)；
Step 3：Closed Strengthen education
By nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, it is placed in closed
Strengthen education in reactor, removal of impurities, filtering obtains leachate and filter residue, and leachate is used into spray-wall interaction technology recovery acid
Liquid is recycled, and by residue washing, B is made in vacuum drying4C nano pipe；
Step 4：Spray-wall interaction
Leachate is atomized, is blown into high temperature pyrolysis stove, is pyrolyzed, nanoscale magnesium and pyrolysis tail is obtained
Gas；Wherein, the hydrogen chloride in pyrolysis tail gas forms hydrochloric acid after absorption, returns to sealing Strengthen education process and recycles；In height
Pyrolysis temperature in warm pyrolysis oven is 200~700 DEG C, and pyrolysis time is 0.5~60min.
In described step 1, the technological parameter of described high energy ball mill is：Pellet mass ratio is 1：(5~30), ball milling
Rotating speed is 150~450rpm, and Ball-milling Time is 15~150min.
In described step 2, the mode of described reaction mass cooling is water cooling or furnace cooling.
In described step 2, the initiation method of described self-propagating reaction is local methods of printing or overall heating；Its
In, local methods of printing refers to local with heating wire heating response block blank in self-propagating reaction stove, initiation self-propagating reaction；
Overall heating refers to block blank integrally heats up in self-propagating reaction stove, untill self-propagating reaction occurs, temperature
Control is at 500~800 DEG C.
In described step 2, described nanotube-shaped B4In combustion product of the C products Dispersed precipitate in MgO matrixes, receive
Mitron shape is two-dimensional nano tubular construction.
In described step 3, the molar concentration of described watery hydrochloric acid is 1~12mol/L.
It is described by nanotube-shaped B in described step 34Combustion product leaching of the C products Dispersed precipitate in MgO matrixes
Enter in watery hydrochloric acid, hydrochloric acid and nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to anti-
The mol ratio of chemical equation is answered, the amount of hydrochloric acid is added 10~40% more than theoretical amount, the chemical equation of reaction institute foundation is
MgO+2HCl=MgCl2+H2O。
In described step 3, the technological parameter of described Strengthen education is：Extraction temperature is 20~80 DEG C, extraction time
For 60~360min.
Described by residue washing in described step 3, vacuum drying concrete operation step is：Leachate will be removed
Filter residue be washed with water to washing lotion for neutrality, then dried under vacuum in vacuum drying oven, drying temperature be 50~120
DEG C, the time is at least 4h.
In described step 4, the mode that described leachate carries out atomization injection is：In 0.13~0.6MPa pressure
Under, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer.
In described step 4, the mass concentration of magnesium chloride is 50~300g/L in described leachate.
In described step 4, the granularity of described nanoscale magnesium is 80~400nm.
In described step 4, the concentration for the hydrochloric acid that described hydrogen chloride is formed after absorption is 1~8mol/L.
A kind of situ-combustion synthesis of the present invention prepares B4The method of C nano pipe, compared to prior art, its Method And Principle
It is with beneficial effect：
1. chemical equation of the present invention is：
The reaction equation of self-propagating synthesis is as follows：2B2O3+ 6Mg+C=B4C+6MgO+ △ H, wherein △ H represent self- propagating
React the reaction heat of generating process reaction release；
Closed Strengthen education process reaction is as follows：MgO+2HCl=MgCl2+H2O；
The reaction of spray-wall interaction process is as follows：MgCl2+H2O=MgO+2HCl.
2. handled by high-energy ball milling boron oxide and magnesium powder powder is subjected to deformation repeatedly, it is cold welding, broken, so as to reach
The level of atomic level alloying between element；At ball milling initial stage, material is repeated extrusion, and by broken, soldering, is squeezed again
Pressure, forms the composite particles of stratiform, and composite particles produce newborn atomic plane, stratiform knot under the continuous effect of mechanical mill power
Structure is constantly refined；In mechanical milling process, the formation of layer structure, the reduction of synusia spacing shortens the interatomic diffusion road of solid-state
Footpath, alloying process accelerates between making element, and powder grain degree substantially diminishes；Substantial amounts of collision phenomenon occurs in mechanical milling process simultaneously
Between ball-powder ball, serious plastic deformation occurs under collision effect for captured powder, makes powder by two collisions
" miniature " forging effect of ball；The high density of defects and nano-interface that ball milling is produced can be big during follow-up self-propagating reaction
The big progress for promoting self-propagating reaction, it is ensured that the conversion ratio and product yield of reaction；Simultaneously after high-energy ball milling is handled
The reaction mass of the high activity state of acquisition has higher self-propagating reaction speed and thermograde, therefore ensure that reaction product
Nanocrystalline size and particle development degree.
The B of the present invention2O3Mechanical activation pretreatment is carried out first with Mg, can obtain B2O3It is very refined and fill with Mg
Divide the presoma of the high activity of disperse combination；The presoma is uniformly mixed with CNT again, can both ensure C nanotube
Pattern is not destroyed, and ensures that boracic presoma obtains mechanical activation again, improves material reaction activity.Mixture enters together
During row self-propagating reaction, boracic presoma is understood itself occurs the ultra-fine high activity B simple substance of strong exothermic reaction generation first；By
In the thermal discharge of superelevation newly-generated B can be triggered to be attached to nanotube-shaped C immediately to carry out combination reaction, directly generate nanometer
The B of tubulose4C products, therefore the morphology controllable of this handicraft product, raw material availability are high.
High-energy ball milling processing, obtains the active presoma of boracic, it is ensured that the carry out degree of reaction, improves reactant
Conversion ratio；Self-propagating reaction pattern is used simultaneously, is taken full advantage of and is reacted the reaction heat of itself, reduces energy consumption；It is simple to operate,
Low, the B of gained is required to process conditions4C nano pipe has purity high, morphology controllable, the advantages of pyroelectricity is good.
3. the leaching process of the present invention is carried out in enclosed high pressure kettle, it is ensured that B4The purity and leaching efficiency of C products；From climing
Prolong that the MgO impurity generated in course of reaction is loose, product is easily broken, MgO impurity reactivity is high, MgO impurity is wrapped in B4C
Surface, beneficial to the leaching of hydrochloric acid.Because acidleach process is carried out in enclosed high pressure kettle, leachate less turbulence is greatly carried
Height, wherein diffusion mass transfer process is also greatly strengthened, so as to ensure that MgO thorough removal, it is ensured that B4C products it is high-purity
Degree., need to be by salt excessive acid, while to ensure clean result, in washing process to ensure that MgO is removed completely in leaching process
Washed using dynamic circulation, i.e., washing lotion keeps constant water level in sink in washing process, how many washing lotion discharge is with regard to how many
Fresh water is supplemented, washing to neutrality.
4. self-propagating reaction of the present invention can be triggered using local methods of printing has easy to operate, the advantage of energy-conservation.
5. handling magnesium chloride solution by the way of spray-wall interaction, reaction efficiency is high, can obtain the production of nanoscale magnesium
Product, improve added value of product, while acid and water that production process is produced can be realized by thermal decomposition process and recycled, realize
Whole process is without useless clean manufacturing.
It is the production technology of clean and effective safety, it is easy to work 6. a process efficient, energy-conservation, flow are short, low for equipment requirements
Industry is promoted.This method may also used to prepare the ceramic nano pipes such as SiC.
Brief description of the drawings
Fig. 1 is the method production B using the present invention4The process chart of C nano pipe.
Embodiment
With reference to embodiment, the present invention is described in further detail.
Boron oxide, magnesium powder, the hydrochloric acid used in following examples is technical grade product.
Boron oxide, magnesium powder, the granularity of carbon dust are respectively less than 0.5mm.
CNT is high-purity single-walled carbon nanotube to commercially produce, 1~50nm of diameter, 1~30 μm of length, according to
Target product requires the CNT model of selection different size.
The self-propagating reaction stove used in following examples self- propagating disclosed in patent " ZL200510047308.2 " is anti-
Stove is answered, the reacting furnace is made up of reaction vessel, heater, sight glass, transformer, function recording instrument, thermocouple, gas valve.
The model for the planetary high-energy ball mill that high-energy ball milling processing is used is Pulveristte4, ball in following examples
Mill rotating speed is 100~450rpm.
The time of self-propagating reaction is 5~90s in following examples.
The drying time that filter residue and drying is handled in following examples is at least 4h.
" metal chloride disclosed in CN 103771344A " is molten for patent for the spray pyrolysis unit used in following examples
Liquid jet is blown rapid pyrolysis apparatus, and the device includes jet pyrolysis system, cyclone separation system, tail gas absorbing system.
Embodiment 1
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, its process chart is shown in Fig. 1, specifically according to the following steps
Carry out：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：3；The technological parameter of high energy ball mill is：Pellet mass ratio is
1：10, rotational speed of ball-mill is 300rpm, and Ball-milling Time is 30min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 10MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
500 DEG C, reaction mass is obtained, after reaction mass furnace cooling, two-dimensional nano tubulose B is obtained4C products Dispersed precipitate is in MgO bases
Combustion product in body；
Wherein, in molar ratio, B2O3：Mg：C=1：3：0.5；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 5mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 80 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 50 DEG C, and the time is 24h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 10% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.2MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 400 DEG C, and pyrolysis time is 10min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 6mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 80nm.
Embodiment 2
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2.5；The technological parameter of high energy ball mill is：Pellet mass ratio
For 1：15, rotational speed of ball-mill is 200rpm, and Ball-milling Time is 60min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 20MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
800 DEG C, reaction mass is obtained, after reaction mass furnace cooling, two-dimensional nano tubulose B is obtained4C products Dispersed precipitate is in MgO bases
Combustion product in body；
Wherein, in molar ratio, B2O3：Mg：C=1：2.5：0.5；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 8mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 80 DEG C of Strengthen education 100min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 120 DEG C, and the time is 4h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 15% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 300g/L in leachate.
Step 4：Spray-wall interaction
Under 0.3MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 500 DEG C, and pyrolysis time is 20min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 3mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 400nm.
Embodiment 3
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：3；The technological parameter of high energy ball mill is：Pellet mass ratio is
1：20, rotational speed of ball-mill is 400rpm, and Ball-milling Time is 100min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 40MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of overall heating, temperature control exists
600 DEG C, reaction mass is obtained, after reaction mass furnace cooling, two-dimensional nano tubulose B is obtained4C products Dispersed precipitate is in MgO bases
Combustion product in body；
Wherein, in molar ratio, B2O3：Mg：C=1：3：0.6；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 10mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 60 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 100 DEG C, and the time is 8h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 15% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 200g/L in leachate.
Step 4：Spray-wall interaction
Under 0.4MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 300 DEG C, and pyrolysis time is 15min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 3mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 300nm.
Embodiment 4
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2.7；The technological parameter of high energy ball mill is：Pellet mass ratio
For 1：8, rotational speed of ball-mill is 250rpm, and Ball-milling Time is 40min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 40MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
600 DEG C, reaction mass is obtained, is passed through into self-propagating reaction stove after cold water to reaction mass cooling, obtains two-dimensional nano tubulose
B4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：2.7：0.5；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 2mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 50 DEG C of Strengthen education 180min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 100 DEG C, and the time is 8h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 40% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 180g/L in leachate.
Step 4：Spray-wall interaction
Under 0.2MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 600 DEG C, and pyrolysis time is 30min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 6mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 350nm.
Embodiment 5
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：4；The technological parameter of high energy ball mill is：Pellet mass ratio is
1：30, rotational speed of ball-mill is 200rpm, and Ball-milling Time is 30min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 30MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
720 DEG C, reaction mass is obtained, is passed through into self-propagating reaction stove after cold water to reaction mass cooling, obtains two-dimensional nano tubulose
B4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：4：0.6；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 10mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 40 DEG C of Strengthen education 120min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 90 DEG C, and the time is 10h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 40% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 180g/L in leachate.
Step 4：Spray-wall interaction
Under 0.5MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 600 DEG C, and pyrolysis time is 15min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 5mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 240nm.
Embodiment 6
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：4；The technological parameter of high energy ball mill is：Pellet mass ratio is
1：5, rotational speed of ball-mill is 450rpm, and Ball-milling Time is 15min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 60MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
720 DEG C, reaction mass is obtained, is passed through into self-propagating reaction stove after cold water to reaction mass cooling, obtains two-dimensional nano tubulose
B4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：4：0.6；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 1mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 80 DEG C of Strengthen education 60min, removal of impurities, filtering obtains leachate and filter residue, will soaked
Go out liquid to recycle using spray-wall interaction technology recovery acid solution, it is neutrality that filter residue is washed with water into washing lotion, then in vacuum
Dried under vacuum in baking oven, drying temperature is 50 DEG C, and the time is 12h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 40% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 300g/L in leachate.
Step 4：Spray-wall interaction
Under 0.6MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 700 DEG C, and pyrolysis time is 0.5min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail
Hydrogen chloride in gas forms the hydrochloric acid that molar concentration is 1mol/L after absorption, returns to sealing Strengthen education process and recycles；
Wherein, nanoscale magnesium is recycled as byproduct, and its granularity is 360nm.
Embodiment 7
A kind of situ-combustion synthesis prepares B4The method of C nano pipe, is carried out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains boracic
Precursor mixture；Wherein, in molar ratio, B2O3：Mg=1：2；The technological parameter of high energy ball mill is：Pellet mass ratio is
1：30, rotational speed of ball-mill is 150rpm, and Ball-milling Time is 150min.
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 10MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers carry out self-propagating reaction in the way of local methods of printing, temperature control exists
720 DEG C, obtain after reaction mass, reaction mass natural cooling, obtain two-dimensional nano tubulose B4C products Dispersed precipitate is in MgO bases
Combustion product in body；
Wherein, in molar ratio, B2O3：Mg：C=1：4：0.6；
Step 3：Closed Strengthen education
By nanotube-shaped B4Combustion product immersion molar concentration of the C products Dispersed precipitate in MgO matrixes is that 12mol/L is dilute
In hydrochloric acid, it is placed in closed reactor, in 20 DEG C of Strengthen education 360min, removal of impurities, filtering obtains leachate and filter residue, will
Leachate reclaims acid solution using spray-wall interaction technology and recycled, and it is neutrality that filter residue is washed with water into washing lotion, then true
Dried under vacuum in empty baking oven, drying temperature is 120 DEG C, and the time is 4h, B is made4C nano pipe；
Wherein, by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid
With nanotube-shaped B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to rubbing for reactive chemistry equation
You compare, and add the amount of hydrochloric acid 10% more than theoretical amount, and the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
Wherein, the mass concentration of magnesia is 50g/L in leachate.
Step 4：Spray-wall interaction
Under 0.13MPa pressure, leachate is carried out into high temperature pyrolysis stove by atomization injection by atomizer, carried out
Pyrolysis, pyrolysis temperature is 200 DEG C, and pyrolysis time is 60min, obtains nanoscale magnesium and pyrolysis tail gas；Wherein, it is pyrolyzed tail gas
In hydrogen chloride the hydrochloric acid that molar concentration is 8mol/L is formed after absorption, return to sealing Strengthen education process and recycle；Its
In, nanoscale magnesium is recycled as byproduct, and its granularity is 80nm.
Claims (10)
1. a kind of situ-combustion synthesis prepares B4The method of C nano pipe, it is characterised in that carry out according to the following steps：
Step 1：Mechanical activation
Boron oxide and magnesium powder are mixed in molar ratio, progress mechanical activation processing in high energy ball mill is put into, obtains before boracic
Drive body mixture；Wherein, in molar ratio, B2O3：Mg=1：(2~4)；
Step 2：Self-propagating synthesis
The precursor mixture of boracic is well mixed in molar ratio with CNT, is put into mould, in 10~60MPa compactings
Into block blank, it is placed in self-propagating reaction stove and triggers progress self-propagating reaction, obtains reaction mass, after reaction mass cooling,
Obtain nanotube-shaped B4Combustion product of the C products Dispersed precipitate in MgO matrixes；
Wherein, in molar ratio, B2O3：Mg：C=1：(2~4)：(0.5~0.6)；
Step 3：Closed Strengthen education
By nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, closed reaction is placed in
Strengthen education in kettle, removal of impurities, filtering obtains leachate and filter residue, and leachate is reclaimed into acid solution using spray-wall interaction technology and followed
Ring is utilized, and by residue washing, B is made in vacuum drying4C nano pipe；
Step 4：Spray-wall interaction
Leachate is atomized, is blown into high temperature pyrolysis stove, is pyrolyzed, nanoscale magnesium and pyrolysis tail gas is obtained；
Wherein, the hydrogen chloride in pyrolysis tail gas forms hydrochloric acid after absorption, returns to sealing Strengthen education process and recycles；In high warm
It is 200~700 DEG C to solve the pyrolysis temperature in stove, and pyrolysis time is 0.5~60min.
2. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 1
In, the technological parameter of described high energy ball mill is：Pellet mass ratio is 1：(5~30), rotational speed of ball-mill is 150~450rpm,
Ball-milling Time is 15~150min.
3. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 2
In, the mode of described reaction mass cooling is water cooling or furnace cooling；
In described step 2, the initiation method of described self-propagating reaction is local methods of printing or overall heating；Wherein, office
Portion's methods of printing refers to local with heating wire heating response block blank in self-propagating reaction stove, initiation self-propagating reaction；It is overall
Heating refers to block blank integrally heats up in self-propagating reaction stove, untill self-propagating reaction occurs, temperature control
At 500~800 DEG C.
4. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 2
In, described nanotube-shaped B4In combustion product of the C products Dispersed precipitate in MgO matrixes, nanotube-shaped is two-dimensional nano pipe
Structure.
5. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 3
In, the molar concentration of described watery hydrochloric acid is 1~12mol/L.
6. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 3
In, it is described by nanotube-shaped B4In combustion product immersion watery hydrochloric acid of the C products Dispersed precipitate in MgO matrixes, hydrochloric acid is with receiving
Mitron shape B4The addition of combustion product of the C products Dispersed precipitate in MgO matrixes, according to mole of reactive chemistry equation
Than adding the amount of hydrochloric acid 10~40% more than theoretical amount, the chemical equation of reaction institute foundation is MgO+2HCl=MgCl2+H2O。
7. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 3
In, the technological parameter of described Strengthen education is：Extraction temperature is 20~80 DEG C, and extraction time is 60~360min.
8. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 3
In, described by residue washing, vacuum drying concrete operation step is：The filter residue for removing leachate is washed with water to washing lotion
For neutrality, then dried under vacuum in vacuum drying oven, drying temperature is 50~120 DEG C, and the time is at least 4h.
9. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 4
In, the mode that described leachate carries out atomization injection is：Under 0.13~0.6MPa pressure, it will be leached by atomizer
Liquid carries out atomization injection into high temperature pyrolysis stove；
In described step 4, the mass concentration of magnesium chloride is 50~300g/L in described leachate.
10. situ-combustion synthesis as claimed in claim 1 prepares B4The method of C nano pipe, it is characterised in that described step 4
In, the granularity of described nanoscale magnesium is 80~400nm；
In described step 4, the concentration for the hydrochloric acid that described hydrogen chloride is formed after absorption is 1~8mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710324507.6A CN107226472A (en) | 2017-05-10 | 2017-05-10 | A kind of situ-combustion synthesis prepares B4The method of C nano pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710324507.6A CN107226472A (en) | 2017-05-10 | 2017-05-10 | A kind of situ-combustion synthesis prepares B4The method of C nano pipe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107226472A true CN107226472A (en) | 2017-10-03 |
Family
ID=59933605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710324507.6A Pending CN107226472A (en) | 2017-05-10 | 2017-05-10 | A kind of situ-combustion synthesis prepares B4The method of C nano pipe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107226472A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574014A (en) * | 2018-10-22 | 2019-04-05 | 西安建筑科技大学 | A kind of B4Fiber C felt and preparation method thereof |
| CN113594442A (en) * | 2021-07-27 | 2021-11-02 | 北京大学 | Preparation method of boron-doped nano silicon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408639A (en) * | 2002-09-23 | 2003-04-09 | 中国科学院长春应用化学研究所 | Process for preparing boron carbide powder |
| CN101298389A (en) * | 2008-06-23 | 2008-11-05 | 东北大学 | Boron-containing additive for carbide refractory and preparation thereof |
| CN103466648A (en) * | 2013-08-28 | 2013-12-25 | 东北大学 | Cleaner production method for preparing superfine powder through self-propagating metallurgy method |
| US20140377160A1 (en) * | 2013-05-31 | 2014-12-25 | University Of Notre Dame Du Lac | Combustion synthesis of graphene and carbonous nanomaterials |
| CN106082230A (en) * | 2016-06-20 | 2016-11-09 | 北京光科博冶科技有限责任公司 | A kind of submicron carbonized boron powder and its production and use |
-
2017
- 2017-05-10 CN CN201710324507.6A patent/CN107226472A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408639A (en) * | 2002-09-23 | 2003-04-09 | 中国科学院长春应用化学研究所 | Process for preparing boron carbide powder |
| CN101298389A (en) * | 2008-06-23 | 2008-11-05 | 东北大学 | Boron-containing additive for carbide refractory and preparation thereof |
| US20140377160A1 (en) * | 2013-05-31 | 2014-12-25 | University Of Notre Dame Du Lac | Combustion synthesis of graphene and carbonous nanomaterials |
| CN103466648A (en) * | 2013-08-28 | 2013-12-25 | 东北大学 | Cleaner production method for preparing superfine powder through self-propagating metallurgy method |
| CN106082230A (en) * | 2016-06-20 | 2016-11-09 | 北京光科博冶科技有限责任公司 | A kind of submicron carbonized boron powder and its production and use |
Non-Patent Citations (1)
| Title |
|---|
| 钱兰等: "硼掺杂对碳纳米管形貌和磁性能的影响", 《功能材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574014A (en) * | 2018-10-22 | 2019-04-05 | 西安建筑科技大学 | A kind of B4Fiber C felt and preparation method thereof |
| CN109574014B (en) * | 2018-10-22 | 2022-04-19 | 西安建筑科技大学 | B4C fiber felt and preparation method thereof |
| CN113594442A (en) * | 2021-07-27 | 2021-11-02 | 北京大学 | Preparation method of boron-doped nano silicon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107129305A (en) | A kind of situ-combustion synthesis prepares B4The method of fiber C | |
| CN104941674B (en) | Catalyst of phosphatization cobalt and its preparation method and application is loaded on a kind of activated carbon | |
| CN106976883A (en) | A kind of situ-combustion synthesis prepares B4The method of C nano powder | |
| CN105289433B (en) | A kind of method of prepare with scale transition metal oxide porous microsphere | |
| CN101428348A (en) | Process for producing spherical submicron metal with hydro-thermal treatment | |
| CN103466648B (en) | A kind of self-spreading metallurgical legal system is for the clean preparation method of superfine powder | |
| CN103950946B (en) | A kind of preparation method of niobium (Nb) boride nano-powder | |
| CN107226472A (en) | A kind of situ-combustion synthesis prepares B4The method of C nano pipe | |
| CN109650358A (en) | A method of quickly graphite phase carbon nitride nanometer rods are prepared without template | |
| CN111377449A (en) | Preparation method of boron carbide nanoparticles | |
| CN103273074B (en) | Process method of continuously producing ultra-fine nickel powder | |
| CN107032318A (en) | A kind of nitrogenous carbon material of sheet and preparation method thereof | |
| CN104776412B (en) | A kind of high temperature superfine powder heat recovery boiler | |
| CN206089050U (en) | Carbon nanotube purification system of retrieval and utilization heat energy | |
| CN102082265A (en) | Method for automatically preparing lithium iron phosphate | |
| CN106241845A (en) | A kind of novel ultrapure ball-aluminium oxide powder preparation method | |
| CN100398454C (en) | New process for preparing high quality Co3O4 | |
| CN112978716B (en) | Preparation method of array type thin-wall small-caliber carbon nano tube | |
| CN101746724A (en) | Method for simultaneously preparing hydrogen and zinc oxide powder | |
| CN108298600A (en) | A kind of environment-friendly preparation method thereof of two dimension hydroxide nano piece | |
| CN106629755A (en) | Supergravity gas-liquid precipitation method for preparing silica nanoparticles based on rice hull ash | |
| CN106623981A (en) | Method for preparing niobium monoxide and niobium powder mixture through plasma decomposition | |
| Liu et al. | Effects of gas pressure and temperature on the synthesis of hollow carbon spheres in argon atmosphere | |
| CN112551601A (en) | Spray pyrolysis preparation method and device of nickel oxide powder | |
| CN115448342B (en) | Boehmite powder and preparation 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 |