CN110002479A - A method of preparing nano bar-shape magnesium fluoride - Google Patents
A method of preparing nano bar-shape magnesium fluoride Download PDFInfo
- Publication number
- CN110002479A CN110002479A CN201910429692.4A CN201910429692A CN110002479A CN 110002479 A CN110002479 A CN 110002479A CN 201910429692 A CN201910429692 A CN 201910429692A CN 110002479 A CN110002479 A CN 110002479A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- magnesium fluoride
- fluoride
- template
- shape
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- 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
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 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
- C01P2004/62—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of methods for preparing nano bar-shape magnesium fluoride, it is template using anodised aluminium, magnesium fluoride presoma or magnesium fluoride are filled into the duct of template, after drying, roasting solidification, product after roasting solidifies is gone template carrying out washing treatment to remove template, then using deionized water carrying out washing treatment template will be gone to remove, it is finally dried to obtain nano bar-shape magnesium fluoride, the diameter of the nano bar-shape magnesium fluoride is in 20-500nm and length is at 0.5-500 μm.Magnesium fluoride prepared by the present invention has special Rod-like shape, when for reaction systems such as exchange chloride for fluoride, dehydrochlorination reaction, de- (adding) hydrogen reaction and isomerization reactions there is very strong anti-caking power to greatly improve catalyst life, has expanded its industrial application.
Description
Technical field
The present invention relates to a kind of methods for preparing nano bar-shape magnesium fluoride.
Background technique
Magnesium fluoride is clear crystal or powder, is a kind of important Inorganic Chemicals, additive, smelting as electrolytic aluminium
Refine the fluxing agent of magnesium metal, titanium pigment applies agent, fluorescent material of cathode-ray screen etc..It is also a kind of colorless and transparent simultaneously
Infrared optical material, have it is wider through model and high transmitance, for make the optical prism in infrared optical system,
Lens and window element.There is apparent Lewis acidity for the magnesium fluoride material surface of Nano grade, it can be separately as solid
Acid catalyst or carrier use, and metal fluoride catalysts are shown more good especially under the reaction environment containing fluorine
Corrosion resistance and stability, such as exchange chloride for fluoride, dehydrochlorination reaction, de- (adding) hydrogen reaction and isomerization reaction are a variety of anti-
Answer system.Since quality requirements of each field to magnesium fluoride are different, the method for preparation is also different.For industrially preparing
The technique of magnesium fluoride is mainly magnesite the preparation method.
If applying magnesium fluoride in catalytic field, it is necessary to condition be to have high specific surface area.Therefore it often prepares
At the particle of Nano grade.Preparation method is mainly the following in catalytic field.
Sol-gel fluoride process, is reacted by metal alkoxide and anhydrous hydrogen fluoride, and metal ion polymerize with fluorine ion
Form M-F-M key and simultaneously form the stable colloidal sol being made of nano metal fluoride particle under suitable conditions, with when
Between extension, these nanoparticles will be connected in series to the gel for being formed together three-D space structure, remove inside gel
Solvent, and porous metal in height ratio surface area fluoride can be obtained after roasting.But the high-ratio surface fluorine of sol-gal process preparation
Change magnesium and be easy sintering at a higher temperature, reduces catalyst activity position, catalyst activity reduction.
Template is a kind of very important technology of nano materials in recent years, is preparing high-specific surface area magnesium fluoride
During using the precipitation method by MgF2It is deposited in porous template, then the hole of specific morphology is obtained by removing template
The porous material being evenly distributed, template used are SiO mostly2Template, the fluorination of the obtained meso-hole structure being ordered into mostly
Magnesium.It is generally spherical or unformed in terms of pattern.
But the magnesium fluoride material of high-specific surface area have larger gibbs surface can, therefore for exchange chloride for fluoride,
Sintering, which easily occurs, when the reaction systems such as dehydrochlorination reaction, de- (adding) hydrogen reaction and isomerization reaction causes to inactivate, and shortening is urged
The agent service life.Application of the magnesium fluoride material on catalytic field is set to take into account high activity and the service life will be extremely difficult.
Also have the research that magnesium fluoride is prepared from magnesia fluorination, but study discovery no matter the magnesia of which kind of high-ratio surface,
The reconstruct of crystal structure will be undergone in fluorination process, specific surface sharply declines, and is unable to get the magnesium fluoride of high-ratio surface.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide one kind with anodised aluminium
(AAO) method for preparing nano bar-shape magnesium fluoride for template, magnesium fluoride is made while having both high activity again very strong anti-burning
Knot ability.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that using anodised aluminium is template, will
Magnesium fluoride presoma or magnesium fluoride are filled into the duct of template, and after drying, roasting solidification, the product after roasting solidifies is passed through
It goes template carrying out washing treatment to remove template, is then finally dried using deionized water carrying out washing treatment with template will be gone to remove
Nano bar-shape magnesium fluoride is obtained, the diameter of the nano bar-shape magnesium fluoride is in 20-500nm and length is at 0.5-500 μm.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that it is described to go template for alkaline solution,
Preferably NaOH aqueous solution；The mass concentration of the NaOH aqueous solution is 30~50%, preferably 40%.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that using magnesium fluoride presoma as raw material, system
The step of standby nano bar-shape magnesium fluoride, is as follows: the template is immersed in 0.5-48h in magnesium fluoride precursor sol, dip time
Preferably 12-24h is adsorbed on magnesium fluoride presoma in the duct of template, then takes out template and wipes template table with filter paper
The colloidal sol in face after being placed in 60~150 DEG C of baking ovens dry 10~15h, is placed in Muffle furnace in nitrogen atmosphere and 250-850 DEG C
Lower roasting 0.5-24h, calcining time are preferably 4-20h, and the product after roasting is successively removed template, deionized water washing, are done
It is dry, obtain the nano bar-shape magnesium fluoride.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that the magnesium fluoride precursor sol uses
Sol-gal process preparation, process are as follows: magnesium metal alkoxide is dissolved in alcohols solvent, adds fluoride aqueous solution, is uniformly mixed,
Then aging 1-12h is stored at room temperature to get magnesium fluoride precursor sol is arrived；Wherein the magnesium metal alkoxide is magnesium methoxide or ethyl alcohol
Magnesium, the alcohols solvent are methanol or ethyl alcohol, and the fluoride aqueous solution is methanol solution, the ethanol solution or water-soluble of HF or villiaumite
Liquid, the villiaumite are sodium fluoride or ammonium fluoride.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that the magnesium fluoride precursor sol uses
Sol-gal process preparation, process are as follows: inorganic metal magnesium salts is dissolved in 60-85 DEG C of distilled water, preparation forms inorganic metal
Magnesium salt solution；Villiaumite is dissolved in 60-85 DEG C of distilled water, preparation forms villiaumite solution, then by the inorganic metal magnesium
Salting liquid and villiaumite solution mix rapidly, and maintain the temperature at 60-85 DEG C, after being uniformly mixed, stand aging 24-48h, i.e.,
Obtain magnesium fluoride precursor sol；Wherein the inorganic metal magnesium salts is magnesium chloride, and the villiaumite is sodium fluoride or ammonium fluoride.Its
The middle presoma dispersibility prepared with sol-gal process is high, is easy to adulterate other microelements.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that using chemical deposition prepare described in receive
The rodlike magnesium fluoride of rice, steps are as follows:
1) precipitating reagent, Fluorine source solution, magnesium source solution and the template are added in reaction kettle simultaneously, in 50-100 DEG C of temperature
And be stirred to react under 4-10kPa pressure, the magnesium fluoride of generation is reacted directly described in Fluorine source and magnesium source under the action of precipitating reagent
It is deposited among the duct of template, reaction time 2-48h；
2) step 1) after reaction, removes the mixed liquor in reaction kettle, filtering, and filter residue is placed in 60~150 DEG C of baking ovens
After dry 10~15h, it is placed in Muffle furnace at nitrogen atmosphere and 250-850 DEG C and roasts 0.5-24h, calcining time is preferably
4-20h, the product after roasting is successively removed template, deionized water washing, dry, obtains the nano bar-shape magnesium fluoride.
Directly magnesium fluoride is deposited in the template using step precipitating, simple to operate, active component not easily runs off.
A kind of method preparing nano bar-shape magnesium fluoride, it is characterised in that in step 1), magnesium source solution is oxidation
Magnesium, magnesium carbonate, magnesium sulfate, magnesium hydroxide, magnesium chloride or magnesium acetate aqueous solution；Fluorine source solution be HF, sodium fluoride, ammonium fluoride or
The aqueous solution or methanol solution of fluosilicic acid；Precipitating reagent is ammonium hydroxide or carbonic acid ammonium.
A kind of preparation method preparing nano bar-shape magnesium fluoride is it is characterized in that the anodised aluminium is high-purity
Alumina foil, purity is 99.998% or more, with a thickness of 0.2-0.9mm.
Compared to other templates, porous anodic alumina template preparation process is simple, and cost is relatively low, and more by adjusting
The technological parameter of hole anodised aluminium can obtain the nano aperture of different-shape structure, to obtain receiving for different-shape structure
Rice material.In addition, rodlike magnesium fluoride can finally be prepared using AAO template, due to its rodlike characteristic, magnesium fluoride resists
Caking power is stronger.
By using above-mentioned technology, compared with prior art the invention has the following advantages that
(1) present invention uses AAO material for template, obtains diameter and length-adjustable fluorine by regulating and controlling AAO template pattern
Change magnesium nanotube, club-shaped material generally has preferable anti-caking power than spheroidal material, thus improves magnesium fluoride nanotube
Anti- caking power.
(2) magnesium fluoride prepared has special Rod-like shape, is being used for exchange chloride for fluoride, dehydrochlorination reaction, is taking off
When the reaction systems such as the reaction of (adding) hydrogen and isomerization reaction there is very strong anti-caking power to greatly improve catalyst life,
Its industrial application is expanded.
Detailed description of the invention
Fig. 1 is the TEM figure of fluorination magnesium products prepared by embodiment 1；
Fig. 2 is the N of the magnesium fluoride of business magnesium fluoride and the preparation of the embodiment of the present invention 1~42Adsorption isotherm comparison diagram；
Fig. 3 is the SEM figure for the AAO template that the embodiment of the present invention 1~20 uses.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
In following embodiment, AAO template be high purity aluminium oxide foil (also referred to as anodised aluminium), purity be 99.998% with
On, with a thickness of 0.5mm, it is purchased from Shanghai Lv Meng Aluminum Co., Ltd.The SEM of the AAO template schemes as shown in figure 3, from Fig. 3
It can be seen that AAO substrate has regular nano pore structure, 160~200nm of pore diameter range, structure feature is suitable as substrate
Materials'use.Magnesium fluoride diameter length and pattern can be effectively adjusted using the template.
1 sol-gal process filling in situ magnesium fluoride of embodiment, comprising the following steps:
S1: weigh magnesium methoxide 2.4g and methanol 50mL be slowly stirred in 500mL beaker be uniformly mixed obtain magnesium methoxide first
Alcoholic solution, and AAO template 0.28g is added, then the HF methanol solution that 50mL concentration is 1mol/L is added dropwise dropwise into mixed solution,
Continue to stand aging 12 hours at room temperature after mixing evenly；
After S2: step S1 stands aging, filtering, the solid being obtained by filtration is placed in 60 DEG C of baking ovens dry 12h, then
It is placed in the solidification of tubular type kiln roasting, roasts solidification process are as follows: under nitrogen atmosphere, be warming up to from room temperature with 10 DEG C/min rate
450 DEG C, cooled to room temperature after 4h is then roasted at 450 DEG C；
S3: the product after step S2 roasting is solidified is put in the plastic beaker of 1000mL cleaning, is added 25mL's
40wt%NaOH aqueous solution is followed by stirring and washing to remove AAO template, and agitator treating temperature is 50 DEG C, then with it is a large amount of go from
Sub- water washing is put in 110 DEG C of baking ovens dry 12h to remove excessive NaOH, by the product after washing to get nano bar-shape is arrived
It is fluorinated magnesium products.The TEM for the nano bar-shape magnesium fluoride that embodiment 1 is prepared schemes as shown in Figure 1, it will be seen from figure 1 that fluorination
Magnesium shows the structure of nano bar-shape.The nano material regularity height of club shaped structure, large specific surface area, this helps to improve material
Anti- caking power and catalytic activity.From figure 1 it appears that the diameter of nano bar-shape magnesium fluoride is in 40~60nm and length
At 1~200 μm.
2 sol-gal process filling in situ magnesium fluoride of embodiment:
The experimentation of embodiment 1 is repeated, the differ in that:
In step S1, the additive amount of AAO template is substituted for 0.45g, and the time for standing aging is substituted for 15 hours；
In step S2, dry temperature is substituted for 120 DEG C in an oven, roasting solidification process replacement are as follows: under nitrogen atmosphere,
450 DEG C are warming up to from room temperature with 10 DEG C/min rate, cooled to room temperature after 6h is then roasted at 450 DEG C.
Remaining step condition repeats embodiment 1, finally obtains nano bar-shape fluorination magnesium products.
3 sol-gal process filling in situ magnesium fluoride of embodiment:
The experimentation of embodiment 1 is repeated, the differ in that:
In step S1, the additive amount of AAO template is substituted for 0.71g, and the time for standing aging is substituted for 18 hours；
In step S2, dry temperature is substituted for 120 DEG C in an oven, roasting solidification process replacement are as follows: under nitrogen atmosphere,
450 DEG C are warming up to from room temperature with 10 DEG C/min rate, cooled to room temperature after 16h is then roasted at 450 DEG C.
Remaining step condition repeats embodiment 1, finally obtains nano bar-shape fluorination magnesium products.
4 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 1 is repeated, the differ in that:
In step S1, the additive amount of AAO template is substituted for 1.42g, and the time for standing aging is substituted for 20 hours；
In step S2, dry temperature is substituted for 120 DEG C in an oven, roasting solidification process replacement are as follows: under nitrogen atmosphere,
500 DEG C are warming up to from room temperature with 10 DEG C/min rate, cooled to room temperature after 10h is then roasted at 500 DEG C.
Remaining step condition repeats embodiment 1, finally obtains nano bar-shape fluorination magnesium products.
The N of magnesium fluoride and business magnesium fluoride prepared by the embodiment of the present invention 1~42Adsorption isotherm comparison diagram such as Fig. 2 institute
Show (wherein business magnesium fluoride is purchased from Aladdin chemical reagent net), the magnesium fluoride and business magnesium fluoride of Examples 1 to 4 preparation
N2Adsorption isotherm, successively respectively as shown in curve b, curve c, curve d, curve e and the curve a in Fig. 2.
The crystal structure and pore structure data result of magnesium fluoride and business magnesium fluoride prepared by the embodiment of the present invention 1~4
As shown in table 1.
Table 1
Table 1 has investigated template additive amount to MgF2The influence of structure, business magnesium fluoride are ordered mesoporous material, specific surface
Product is 120m2/ g, aperture are about 10nm.With Al2O3For the MgF of template preparation2For orderly mesoporous material.Fig. 2 gives business
The N of magnesium fluoride and the magnesium fluoride sample of difference AAO template additive amount preparation2Adsorption isotherm, it will thus be seen that the method for the present invention
The adsorption isotherm of the magnesium fluoride sample of preparation is all typical V-type.There is preferable H1 type between relative pressure 0.4-0.8
Hysteresis loop illustrates that material has the central hole structure of even aperture distribution, can also obtain this conclusion by BJH graph of pore diameter distribution, adjusts
AAO template additive amount increases to 1.42g from 0.28g, can respectively obtain the mesoporous material that aperture is 3-3.6nm, specific surface
Additive amount first increases and then decreases of the product with AAO template, MgF prepared by embodiment 22Specific surface area it is maximum, be 304m2/g。
5 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 1 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 24 hours；
In step S2, dry temperature is substituted for 120 DEG C in an oven, roasting solidification process replacement are as follows: under nitrogen atmosphere,
500 DEG C are warming up to from room temperature with 15 DEG C/min rate, then roasts 20h at 500 DEG C.
Remaining step condition repeats embodiment 1, finally obtains nano bar-shape fluorination magnesium products.
6 sol-gal process of embodiment fills magnesium fluoride, comprising the following steps:
S1: it weighs magnesium chloride 11.8g and distilled water 100mL and is placed in thermostat water bath in 500mL beaker and be heated to 75
DEG C, form solution A；It weighs sodium fluoride 9g and distilled water 100mL and is placed in thermostat water bath in 500mL beaker and be heated to 75
DEG C, form solution B；Then solution A and solution B are mixed rapidly, is stood at 75 DEG C after twenty minutes, continue to be stirred
It is even, it is then allowed to stand aging 24 hours, obtains magnesium fluoride precursor sol；
S2: by the AAO template direct impregnation of 1.18g 12 hours in the magnesium fluoride precursor sol obtained by step S1, then
It takes out AAO template and wipes the colloidal sol on its surface with filter paper, be placed in 120 DEG C of baking ovens dry 12h；
S3: after drying to step S2, AAO template is placed in the solidification of tubular type kiln roasting, roasts solidification process are as follows:
Under nitrogen atmosphere, 500 DEG C are warming up to from room temperature with 15 DEG C/min rate, naturally cools to room after then roasting 20h at 500 DEG C
Temperature；
S4: the product after step S3 roasting is put in the plastic beaker of 1000mL cleaning, the 40wt% of 25mL is added
For NaOH aqueous solution agitator treating to remove template AAO, agitator treating temperature is 50 DEG C, then with a large amount of deionized water wash with
Excessive NaOH is removed, the product after washing is put in 110 DEG C of baking ovens dry 12h and is fluorinated magnesium products to get to nano bar-shape.
7 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 6 is repeated, the differ in that:
In step S2, the time that AAO template impregnates in magnesium fluoride precursor sol is substituted for 24 hours；
It in step S3, roasts cured process and is substituted for: under nitrogen atmosphere, being warming up to from room temperature with 10 DEG C/min rate
450 DEG C, 16h then is roasted at 450 DEG C.
Remaining step is same as Example 6, finally obtains nano bar-shape fluorination magnesium products.
8 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 6 is repeated, the differ in that:
The process of step S1 is replaced are as follows: weighs magnesium chloride 11.8g and distilled water 100mL is placed in constant temperature in 500mL beaker
It is heated to 80 DEG C in water-bath, forms solution A；It weighs sodium fluoride 9g and distilled water 100mL is placed in thermostatted water in 500mL beaker
It is heated to 80 DEG C in bath, forms solution B；Then solution A and solution B are mixed rapidly, stands after twenty minutes, continues at 80 DEG C
It is uniformly mixed, is then allowed to stand aging 24 hours, obtain magnesium fluoride precursor sol；
In step S2, the time that AAO template impregnates in magnesium fluoride precursor sol is substituted for 24 hours；
It in step S3, roasts cured process and is substituted for: under nitrogen atmosphere, being warming up to from room temperature with 10 DEG C/min rate
450 DEG C, 16h then is roasted at 450 DEG C.
Remaining step is same as Example 6, finally obtains nano bar-shape fluorination magnesium products.
9 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 6 is repeated, the differ in that:
The process of step S1 is replaced are as follows: weighs magnesium chloride 11.8g and distilled water 100mL is placed in constant temperature in 500mL beaker
It is heated to 70 DEG C in water-bath, forms solution A；It weighs sodium fluoride 9g and distilled water 100mL is placed in thermostatted water in 500mL beaker
It is heated to 70 DEG C in bath, forms solution B；Then solution A and solution B are mixed rapidly, stands after twenty minutes, continues at 70 DEG C
It is uniformly mixed, is then allowed to stand aging 24 hours, obtain magnesium fluoride precursor sol；
In step S2, the time that AAO template impregnates in magnesium fluoride precursor sol is substituted for 36 hours；
It in step S3, roasts cured process and is substituted for: under nitrogen atmosphere, being warming up to from room temperature with 10 DEG C/min rate
500 DEG C, 10h then is roasted at 500 DEG C.
Remaining step is same as Example 6, finally obtains nano bar-shape fluorination magnesium products.
10 sol-gal process of embodiment fills magnesium fluoride, comprising the following steps:
S1: weigh magnesium methoxide 2.4g and methanol 50mL be slowly stirred in 500mL beaker be uniformly mixed obtain magnesium methoxide first
Alcoholic solution, then the HF methanol solution that 50mL concentration is 1mol/L is added dropwise dropwise into the magnesium methoxide methanol solution, continue to stir
Aging is stored at room temperature 13 hours after uniformly, obtains magnesium fluoride precursor sol；
S2: and then by the AAO template direct impregnation of 0.32g 12 hours in the magnesium fluoride precursor sol obtained by step S1,
It then takes out AAO template and wipes the colloidal sol of AAO template surface with filter paper, be placed in 60 DEG C of baking ovens dry 12h；
S3: after drying to step S2, AAO template is placed in the solidification of tubular type kiln roasting, roasts solidification process are as follows:
Under nitrogen atmosphere, 450 DEG C are warming up to from room temperature with 10 DEG C/min rate, naturally cools to room after then roasting 4h at 450 DEG C
Temperature；
S4: the product after step S3 roasting is put in the plastic beaker of 1000mL cleaning, the 40wt% of 25mL is added
For NaOH aqueous solution agitator treating to remove template AAO, agitator treating temperature is 50 DEG C, then with a large amount of deionized water wash with
Excessive NaOH is removed, the product after washing is put in 110 DEG C of baking ovens dry 12h and is fluorinated magnesium products to get to nano bar-shape.
11 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 10 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 20 hours；
The process of step S2 is substituted for: by the AAO template direct impregnation of 0.42g 6 hours in magnesium fluoride precursor sol,
It then takes out AAO template and wipes the colloidal sol of AAO template surface with filter paper, be placed in 120 DEG C of baking ovens dry 12h；
In step S3, roasting solidification process replacement are as follows: under nitrogen atmosphere, be warming up to 450 from room temperature with 10 DEG C/min rate
DEG C, cooled to room temperature after 6h is then roasted at 450 DEG C；
Remaining step is same as in Example 10, finally obtains nano bar-shape fluorination magnesium products.
12 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 10 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 15 hours；
The process of step S2 is substituted for: the AAO template direct impregnation of 0.52g is 24 small in magnesium fluoride precursor sol
When, it then takes out AAO template and wipes the colloidal sol of AAO template surface with filter paper, be placed in 120 DEG C of baking ovens dry 12h；
In step S3, roasting solidification process replacement are as follows: under nitrogen atmosphere, be warming up to 450 from room temperature with 10 DEG C/min rate
DEG C, cooled to room temperature after 16h is then roasted at 450 DEG C；
Remaining step is same as in Example 10, finally obtains nano bar-shape fluorination magnesium products.
13 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 10 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 48 hours；
The process of step S2 is substituted for: the AAO template direct impregnation of 0.32g is 36 small in magnesium fluoride precursor sol
When, it then takes out AAO template and wipes the colloidal sol of AAO template surface with filter paper, be placed in 120 DEG C of baking ovens dry 12h；
It in step S3, roasts cured process and is substituted for: under nitrogen atmosphere, being warming up to from room temperature with 10 DEG C/min rate
500 DEG C, cooled to room temperature after 10h is then roasted at 500 DEG C；
Remaining step is same as in Example 10, finally obtains nano bar-shape fluorination magnesium products.
14 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 13 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 24 hours；Remaining step is identical as embodiment 13, finally obtains and receives
The rodlike fluorination magnesium products of rice.
15 sol-gal process of embodiment fills magnesium fluoride:
The experimentation of embodiment 10 is repeated, the differ in that:
In step S1, the time for standing aging is substituted for 36 hours；
The process of step S2 is substituted for: the AAO template direct impregnation of 0.32g is 48 small in magnesium fluoride precursor sol
When, it then takes out AAO template and wipes the colloidal sol of AAO template surface with filter paper, be placed in 120 DEG C of baking ovens dry 12h；
It in step S3, roasts cured process and is substituted for: under nitrogen atmosphere, being warming up to from room temperature with 15 DEG C/min rate
500 DEG C, cooled to room temperature after 20h is then roasted at 500 DEG C；
Remaining step is same as in Example 10, finally obtains nano bar-shape fluorination magnesium products.
16 chemical deposition filling in situ magnesium fluoride of embodiment, comprising the following steps:
S1: by magnesium chloride 10g and ammonium fluoride aqueous solution 68.5mL, (the F concentration of element in ammonium fluoride aqueous solution is 100g/
L it) is fitted into reaction kettle, reaction kettle is sealed and vacuum is extracted to reaction kettle, control reacting kettle inner pressure is 5000Pa, and control is anti-
The temperature for answering mixed liquor in kettle is 95 DEG C, is stirred to react 12 hours；
S2: step S1 after reaction, the mixed liquor in reaction kettle is filtered, filter residue is magnesium fluoride ointment.By gained
Magnesium fluoride ointment is washed repeatedly with 50 DEG C of distilled water, removes the NH of magnesium fluoride ointment adsorption4+、Cl-Then plasma will
Magnesium fluoride ointment after washing is uniformly mixed with the AAO template of 1g, and obtained solid mixture is placed in 200 DEG C of baking ovens and dries water
Point；
S3: by the plastic beaker of the product 1000mL cleaning after step S drying, the 40wt%NaOH that 25mL is added is water-soluble
For liquid agitator treating to remove template AAO, agitator treating temperature is 50 DEG C, is then washed with a large amount of deionized water to remove excess
NaOH, the product after washing is put in 110 DEG C of baking ovens dry 12h and is fluorinated magnesium products to get to nano bar-shape.
17 chemical deposition filling in situ magnesium fluoride of embodiment:
The experimentation of embodiment 16 is repeated, the differ in that:
Process in step S1 is substituted for: by magnesium chloride 10g and ammonium fluoride aqueous solution 68.5mL (in ammonium fluoride aqueous solution
F concentration of element be 100g/L) is fitted into reaction kettle, by reaction kettle seal and to reaction kettle extract vacuum, control reaction kettle in
Pressure is 6000Pa, and the temperature for controlling mixed liquor in reaction kettle is 97 DEG C, is stirred to react 14 hours；Remaining step and embodiment 16
It is identical, finally obtain nano bar-shape fluorination magnesium products.
18 chemical deposition filling in situ magnesium fluoride of embodiment:
The experimentation of embodiment 16 is repeated, the differ in that:
Process in step S1 is substituted for: by magnesium chloride 10g and ammonium fluoride aqueous solution 68.5mL (in ammonium fluoride aqueous solution
F concentration of element be 100g/L) is fitted into reaction kettle, by reaction kettle seal and to reaction kettle extract vacuum, control reaction kettle in
Pressure is 6500Pa, and the temperature for controlling mixed liquor in reaction kettle is 97 DEG C, is stirred to react 16 hours；
In step S2, the temperature that solid mixture is dried in an oven is substituted for 300 DEG C；Remaining step and embodiment
16 is identical, finally obtains nano bar-shape fluorination magnesium products.
19 chemical deposition filling in situ magnesium fluoride of embodiment:
The experimentation of embodiment 16 is repeated, the differ in that:
Process in step S1 is substituted for: by magnesium chloride 10g and ammonium fluoride aqueous solution 68.5mL (in ammonium fluoride aqueous solution
F concentration of element be 100g/L) is fitted into reaction kettle, by reaction kettle seal and to reaction kettle extract vacuum, control reaction kettle in
Pressure is 6500Pa, and the temperature for controlling mixed liquor in reaction kettle is 100 DEG C, is stirred to react 24 hours；
Process in step S2 is substituted for: after reaction, the mixed liquor in reaction kettle is filtered by step S1, and filter residue is
Magnesium fluoride ointment.Gained magnesium fluoride ointment is washed repeatedly with 70 DEG C of distilled water, removes the NH of magnesium fluoride ointment adsorption4 +、Cl-Then magnesium fluoride ointment after washing is uniformly mixed by plasma with the AAO template of 1g, obtained solid mixture is placed in
Moisture is dried in 300 DEG C of baking ovens；Remaining step is identical as embodiment 16, finally obtains nano bar-shape fluorination magnesium products.
20 chemical deposition filling in situ magnesium fluoride of embodiment
The experimentation of embodiment 16 is repeated, the differ in that:
Process in step S1 is substituted for: by magnesium chloride 10g and ammonium fluoride aqueous solution 68.5mL (in ammonium fluoride aqueous solution
F concentration of element be 100g/L) is fitted into reaction kettle, by reaction kettle seal and to reaction kettle extract vacuum, control reaction kettle in
Pressure is 9000Pa, and the temperature for controlling mixed liquor in reaction kettle is 97 DEG C, is stirred to react 16 hours；
Process in step S2 is substituted for: after reaction, the mixed liquor in reaction kettle is filtered by step S1, and filter residue is
Magnesium fluoride ointment.Gained magnesium fluoride ointment is washed repeatedly with 70 DEG C of distilled water, removes the NH of magnesium fluoride ointment adsorption4 +、Cl-Then magnesium fluoride ointment after washing is uniformly mixed by plasma with the AAO template of 1g, obtained solid mixture is placed in
Moisture is dried in 300 DEG C of baking ovens；Remaining step is identical as embodiment 16, finally obtains nano bar-shape fluorination magnesium products.
Embodiment 21:
Nano bar-shape magnesium fluoride and commodity magnesium fluoride (chemical formula MgF prepared by Examples 1 to 202, it is purchased from me
Fourth chemical reagent net) it is applied to the reaction that catalysis R-152a dehydrofluorination prepares a vinyl fluoride.Catalysis reaction is anti-in fixed bed
It answers in device and carries out, loadings of the catalyst in fixed bed reactors are 2mL, inventory of the reactant in fixed bed reactors
Are as follows: R-152a 25mL/min, N2For 20mL/min.
Variety classes catalyst (i.e. the nano bar-shape magnesium fluoride and business magnesium fluoride of the preparation of Examples 1 to 2 0), reaction
R-152a conversion ratio, the reaction result of vinyl fluoride selectivity after temperature, reaction 2h is as shown in table 2.
Table 2
As seen from Table 2, with the increase of reaction temperature, catalyst increases the catalytic activity of R-152 dehydrofluorination, and former
Conversion ratio is expected all 60% or more, and selectivity has higher conversion ratio compared to business magnesium fluoride, roast simultaneously 97% or more
It burns temperature and also affects catalytic performance to a certain extent.
Above-mentioned catalysis R-152a dehydrofluorination prepares the reaction of a vinyl fluoride after 50h reacts, and compares catalyst anti-
The grain size variation for answering front and back, being specifically shown in Table 3, (in table 3, grain size refers to fresh catalyst in N before reacting2Atmosphere and reaction
At a temperature of preheat 2h grain size, after reaction grain size refer to fresh catalyst reaction 50h after grain size).Pass through
Compare influence discovery of the differential responses temperature to business magnesium fluoride specific surface and aperture, the present invention prepares magnesium fluoride using template
During product, calcination temperature is affected to the crystal grain of magnesium fluoride.And business magnesium fluoride grain size is with reaction temperature
Increase, variation is obvious, and increasing degree is high, easy-sintering.In reaction temperature from during rising to 350 DEG C for 200 DEG C, the present invention is sharp
The magnesium fluoride grain size rate of rise prepared with template is slow, and crystal grain variation is small, it is not easy to be sintered.
The MgF prepared by the present invention of table 32From BET data of the commodity magnesium fluoride before and after the reaction of different maturing temperatures
Since sintering of catalyst will lead to active reduction, and the present invention has preferable resist by magnesium fluoride prepared by template
Caking power, therefore compared to business magnesium fluoride, magnesium fluoride produced herein has longer service life.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (8)
1. a kind of method for preparing nano bar-shape magnesium fluoride, it is characterised in that using anodised aluminium is template, before magnesium fluoride
It drives body or magnesium fluoride is filled into the duct of template, after drying, roasting solidification, roast the product after solidifying through removing template
Then carrying out washing treatment is finally dried to obtain nanometer using deionized water carrying out washing treatment to remove template template will be gone to remove
Rodlike magnesium fluoride, the diameter of the nano bar-shape magnesium fluoride is in 20-500nm and length is at 0.5-500 μm.
2. a kind of method for preparing nano bar-shape magnesium fluoride as described in claim 1, it is characterised in that described to go the template to be
Alkaline solution, preferably NaOH aqueous solution；The mass concentration of the NaOH aqueous solution is 30 ~ 50%, preferably 40%.
3. a kind of method for preparing nano bar-shape magnesium fluoride as described in claim 1, it is characterised in that with magnesium fluoride presoma
For raw material, the step of preparing nano bar-shape magnesium fluoride, is as follows:
The template is immersed in 0.5-48h in magnesium fluoride precursor sol, dip time is preferably 12-24h, before making magnesium fluoride
It drives body to be adsorbed in the duct of template, then takes out template and wipe the colloidal sol of template surface with filter paper, be placed in 60 ~ 150 DEG C of bakings
In case after dry 10 ~ 15h, it is placed in Muffle furnace at nitrogen atmosphere and 250-850 DEG C and roasts 0.5-24h, calcining time is excellent
It is selected as 4-20h, the product after roasting is successively removed template, deionized water washing, and it is dry, obtain the nano bar-shape fluorination
Magnesium.
4. a kind of method for preparing nano bar-shape magnesium fluoride as claimed in claim 3, it is characterised in that the magnesium fluoride forerunner
Body colloidal sol is prepared using sol-gal process, process are as follows: magnesium metal alkoxide is dissolved in alcohols solvent, adds fluoride aqueous solution, is stirred
It mixes uniformly mixed, is stored at room temperature aging 1-12h then to get to magnesium fluoride precursor sol；Wherein the magnesium metal alkoxide is
Magnesium methoxide or magnesium ethylate, the alcohols solvent are methanol or ethyl alcohol, and the fluoride aqueous solution is methanol solution, the second of HF or villiaumite
Alcoholic solution or aqueous solution, the villiaumite are sodium fluoride or ammonium fluoride.
5. a kind of method for preparing nano bar-shape magnesium fluoride as claimed in claim 3, it is characterised in that the magnesium fluoride forerunner
Body colloidal sol is prepared using sol-gal process, process are as follows: inorganic metal magnesium salts is dissolved in 60-85 DEG C of distilled water, prepares shape
At inorganic metal magnesium salt solution；Villiaumite is dissolved in 60-85 DEG C of distilled water, preparation forms villiaumite solution, then will be described
Inorganic metal magnesium salt solution and villiaumite solution mix rapidly, and maintain the temperature at 60-85 DEG C, after being uniformly mixed, stand old
Change 24-48h to get magnesium fluoride precursor sol is arrived；Wherein the inorganic metal magnesium salts is magnesium chloride, and the villiaumite is sodium fluoride
Or ammonium fluoride.
6. a kind of method for preparing nano bar-shape magnesium fluoride as described in claim 1, it is characterised in that use chemical deposition
The nano bar-shape magnesium fluoride is prepared, steps are as follows:
1) precipitating reagent, Fluorine source solution, magnesium source solution and the template are added in reaction kettle simultaneously, in 50-100 DEG C of temperature and 4-
It is stirred to react under 10 kPa pressure, the magnesium fluoride of generation is reacted directly in the template in Fluorine source and magnesium source under the action of precipitating reagent
Duct among deposit, reaction time 2-48h；
2) step 1) after reaction, removes the mixed liquor in reaction kettle, filtering, and filter residue is placed in 60 ~ 150 DEG C of baking ovens dry 10
After ~ 15h, it is placed in Muffle furnace at nitrogen atmosphere and 250-850 DEG C and roasts 0.5-24h, calcining time is preferably 4-20h,
Product after roasting is successively removed template, deionized water washing, dry, obtains the nano bar-shape magnesium fluoride.
7. a kind of method for preparing nano bar-shape magnesium fluoride as claimed in claim 6, it is characterised in that in step 1), magnesium source is molten
Liquid is the aqueous solution of magnesia, magnesium carbonate, magnesium sulfate, magnesium hydroxide, magnesium chloride or magnesium acetate；Fluorine source solution be HF, sodium fluoride,
The aqueous solution or methanol solution of ammonium fluoride or fluosilicic acid；Precipitating reagent is ammonium hydroxide or carbonic acid ammonium.
8. a kind of preparation method for preparing nano bar-shape magnesium fluoride is it is characterized in that the anodic oxygen according to patent requirements 1
Change aluminium is high purity aluminium oxide foil, and purity is 99.998% or more, with a thickness of 0.2-0.9mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910429692.4A CN110002479B (en) | 2019-05-22 | 2019-05-22 | Method for preparing nano-rod-shaped magnesium fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910429692.4A CN110002479B (en) | 2019-05-22 | 2019-05-22 | Method for preparing nano-rod-shaped magnesium fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110002479A true CN110002479A (en) | 2019-07-12 |
| CN110002479B CN110002479B (en) | 2021-06-29 |
Family
ID=67177655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910429692.4A Active CN110002479B (en) | 2019-05-22 | 2019-05-22 | Method for preparing nano-rod-shaped magnesium fluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110002479B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114082386A (en) * | 2021-12-06 | 2022-02-25 | 大连理工大学 | Device and method for semi-continuously synthesizing high-purity magnesium fluoride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624208A (en) * | 2009-07-31 | 2010-01-13 | 天津大学 | Method for preparing zinc oxide nanowire array based on coordination chemical reaction theory |
| CN103482661A (en) * | 2013-09-30 | 2014-01-01 | 浙江工业大学 | Synthetic method of nanometer magnesium fluoride with high specific surface area |
| CN105107533A (en) * | 2015-08-18 | 2015-12-02 | 巨化集团技术中心 | Preparation method for gaseous-phase dehydrofluorination catalyst |
| CN108083344A (en) * | 2017-12-25 | 2018-05-29 | 浙江工业大学 | The method that template-hydro-thermal method prepares ferriferrous oxide nano line |
-
2019
- 2019-05-22 CN CN201910429692.4A patent/CN110002479B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624208A (en) * | 2009-07-31 | 2010-01-13 | 天津大学 | Method for preparing zinc oxide nanowire array based on coordination chemical reaction theory |
| CN103482661A (en) * | 2013-09-30 | 2014-01-01 | 浙江工业大学 | Synthetic method of nanometer magnesium fluoride with high specific surface area |
| CN105107533A (en) * | 2015-08-18 | 2015-12-02 | 巨化集团技术中心 | Preparation method for gaseous-phase dehydrofluorination catalyst |
| CN108083344A (en) * | 2017-12-25 | 2018-05-29 | 浙江工业大学 | The method that template-hydro-thermal method prepares ferriferrous oxide nano line |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114082386A (en) * | 2021-12-06 | 2022-02-25 | 大连理工大学 | Device and method for semi-continuously synthesizing high-purity magnesium fluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110002479B (en) | 2021-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Buelna et al. | Sol–gel-derived mesoporous γ-alumina granules | |
| US8357628B2 (en) | Inorganic/organic hybrid totally porous metal oxide particles, methods for making them and separation devices using them | |
| EP1314695B1 (en) | Silica and method for producing the same | |
| CN102583255B (en) | Method for preparing mesoporous composite transition metal oxide | |
| CN106475127A (en) | A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof | |
| CN101704538A (en) | Hydrothermal method for preparing series of special-shaped graded pseudo-boehmite | |
| CN104860341B (en) | A kind of preparation method of high temperature resistant and high specific surface aluminium | |
| CN109999902A (en) | The supported porous grade titanium-silicon molecular sieve catalyst of encapsulation type platinum family sub-nanometer metal and its preparation and application | |
| US20130165608A1 (en) | Catalyst carrier based on silica gel | |
| CN101492170A (en) | Method of manufacturing mesoporous nano- aluminum oxide | |
| CN110813300A (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
| JPS5814365B2 (en) | Manufacturing method of spherical alumina | |
| CN102126949B (en) | Method for synthesizing methyl acrylate | |
| CN110002479A (en) | A method of preparing nano bar-shape magnesium fluoride | |
| CN112811411B (en) | Bowl-shaped mesoporous carbon microsphere and preparation method and application thereof | |
| WO2007105705A1 (en) | Visible light-responsive photocatalyst, method for producing same, photocatalyst coating agent using same, and photocatalyst dispersion | |
| CN109647404A (en) | Yolk/shell type catalyst and preparation method thereof produces hydrogen application with catalysis | |
| CN110545917A (en) | Porous monolith comprising TiO2 and method for producing same | |
| CN105948111B (en) | The preparation method of particular crystal plane titanic oxide material | |
| CN114426300A (en) | Preparation method of macroporous alumina carrier | |
| CN108855209B (en) | Copper-zinc alloy supported hierarchical porous titanium silicalite molecular sieve catalytic material and preparation method thereof | |
| JP5093647B2 (en) | Method for producing metal oxide porous body having mesopores and micropores, metal oxide porous body having mesopores and micropores, and gas purification material using the same | |
| JP4002497B2 (en) | Metal oxide sol and method for producing the same | |
| You et al. | Influence of chelating agent and reaction time on the swelling process for preparation of porous TiO2 particles | |
| GB2038298A (en) | Manufacture of high surface area spheroidal alumina particles having a high average bulk density |
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 |