CN110002725A - The preparation method of porous glass beads, the porous glass beads by this method preparation and its application - Google Patents
The preparation method of porous glass beads, the porous glass beads by this method preparation and its application Download PDFInfo
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- CN110002725A CN110002725A CN201910313598.2A CN201910313598A CN110002725A CN 110002725 A CN110002725 A CN 110002725A CN 201910313598 A CN201910313598 A CN 201910313598A CN 110002725 A CN110002725 A CN 110002725A
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- 239000011324 bead Substances 0.000 title claims abstract description 70
- 239000005373 porous glass Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 157
- 239000000843 powder Substances 0.000 claims abstract description 92
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003814 drug Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000001413 cellular effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000003628 erosive effect Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000005385 borate glass Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/108—Forming porous, sintered or foamed beads
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to a kind of preparation method of porous glass beads, the porous glass beads by this method preparation and its applications.The preparation method processing step is as follows: by the glass of the first acidproof level and the glass preparation substrate glass of the second acidproof level, and by described matrix glass crush, be ground up, sieved, obtain substrate glass powder；Described matrix glass powder is mixed in proportion with interleaving agent, is heated to 900~1000 DEG C, is kept the temperature, it is cooling, obtain glass microballoon；The glass microballoon is placed in acid solution and is corroded, is cleaned, drying obtains porous glass beads.The preparation method of the porous glass beads passes through the ratio and sour etching technique of the first glass powder and the second glass powder, obtain the porous glass beads of different pore size and porosity, and even aperture distribution, the porous glass beads being easy between preparation aperture 500nm~1 μm, particularly useful as adsorption sustained-release material, it is widely used in the fields such as medicine, environmental protection, the energy, building materials.
Description
Technical field
The present invention relates to glass microballoon manufacturing field, in particular to a kind of preparation method of porous glass beads, by the party
The porous glass beads of method preparation and its application.
Background technique
Porous glass beads due to its with large specific surface area, thermodynamic stability is good, chemical stability is good, intensity is high,
It is unlikely to deform, loads the features such as good with separating property, be absorption, the slow-release material of a kind of function admirable, the spy different according to its
Point can be used in the fields such as slow releasing carrier of medication, catalyst carrier, sewage treatment, hydrogen storage.
Porous glass beads in the prior art are prepared by melt phase-separation, with SiO2、Na2CO3、
H3BO3Substrate glass is prepared Deng for primary raw material, obtained substrate glass is isolated after being ground into certain granularity by addition
Agent is heated to melting, its mitochondrial surface is enabled to shrink glomeration, be sieved into after the different matrix microballon of particle size carry out hot split-phase,
Sour dissolved washes, is dried to obtain porous glass beads.
Pore size, distributing homogeneity, porosity of the porous glass beads prepared according to the method described above etc. each depend on
The quality of high temperature split-phase situation.It usually requires to be kept for a few houres to tens hours at a constant temperature.Preparation process is complicated, work
Skill stability is poor.The porous size of preparation is difficult to obtain the porous structure of 500nm or more in 10nm~300nm.In catalyst or
When the fixation and separation of drug molecule, it be easy to cause duct to block, influences using effect.
Summary of the invention
The first purpose of this invention is to propose that a kind of preparation process is simple, technology stability is good and pore-size is controlled
Porous glass beads preparation method.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of porous glass beads preparation method, processing step is as follows:
1) by the glass preparation substrate glass of the glass of the first acidproof level and the second acidproof level, and by the matrix
Glass is crushed, is ground up, sieved, and obtains substrate glass powder；
2) the substrate glass powder is mixed in proportion with interleaving agent, is heated to 900~1000 DEG C, heat preservation is cold
But, it is rinsed with water and removes interleaving agent, obtain glass microballoon；
3) glass microballoon is placed in acid solution and is corroded, taken out, cleaned, is filtered by vacuum, drying obtains cellular glass
Microballon.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of the porous glass beads, wherein the preparation of the substrate glass includes following
Step:
A, the glass material of the first acidproof level is crushed, is ground, sieving obtains the first glass powder of partial size≤10 μm；
B, the glass material of the second acidproof level is crushed, is ground, sieving obtains the second glass powder of partial size≤10 μm；
C, first glass powder and the second glass powder are mixed in proportion, obtains glass powder mixture；
D, the glass powder mixture is transferred in mold, in certain temperature, certain pressure and certain vacuum item
It is sintered and cooled under part to room temperature, moves back mould, obtain substrate glass.
Preferably, the preparation method of the porous glass beads, wherein the first glass powder and the second glass in step C
Before powder mixing, need to the first glass powder and the second glass powder be cleaned and be dried；First glass powder and second in step C
The mixed proportion of glass powder is 1:10~50 in mass.
Preferably, the preparation method of the porous glass beads, wherein glass powder mixture described in step D
Sintering temperature is higher than its glass transition temperature；The vacuum degree of system is 0.1Pa~100Pa, glass powder mixture institute when sintering
The pressure received is 20~50MPa；Its sintering temperature is 800 DEG C~900 DEG C, and sintering time is 0.5~4h.
Preferably, the preparation method of the porous glass beads, the wherein partial size of the sieve of sieving described in step 1)
Including≤30 μm, 30~50 μm, 50~100 μm, 100~200 μm, 200~300 μm, 300~400 μm and 400~500 μm.
Preferably, the preparation method of the porous glass beads, wherein interleaving agent described in step 2) is selected from graphite powder
Or at least one of MgO powder；The mixed proportion of substrate glass powder and interleaving agent is 1:2~10 in mass.
Preferably, the preparation method of the porous glass beads, wherein acid solution described in step 3) is selected from nitric acid, salt
At least one of acid and sulfuric acid；The concentration of the acid solution is 0.1mol/L~1mol/L；The temperature of acid solution when corrosion
It is 30 DEG C~80 DEG C, etching time is 0.5h~5h.
Preferably, the preparation method of the porous glass beads, wherein cleaning described in step 3) be will be through excessive erosion
Glass microballoon cleaned 2 times~5 times using deionized water, then be soaked in ethyl alcohol, propyl alcohol or isopropanol and keep 15min
~60min；It takes out and dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 0.5h~1h.
Second object of the present invention is to propose a kind of porous glass beads prepared using preparation method above-mentioned, institute
The size that can according to need adjustment aperture for the porous glass beads stated, porous particle size and distribution can bases
Actual needs is adjusted.
Third object of the present invention is to propose that a kind of porous glass beads using preparation method above-mentioned preparation exist
The fixation of catalyst or drug molecule and the application of separation field.
By above-mentioned technical proposal, a kind of preparation method of porous glass beads proposed by the present invention is prepared by this method
Porous glass beads and its application at least have the advantage that
1, the preparation method of porous glass beads proposed by the present invention differs greatly which employs two kinds of acid-resistant stabilities
Substrate glass is prepared in glass powder mixing and sintering, then by processing steps such as substrate glass crushing, Cheng Zhu, corrosion, changes
Traditional melting split-phase technique by the ratio and acid corrosion technological parameter of the first glass powder and the second glass powder can
Very easily to obtain the porous glass beads of different pore size and porosity, and even aperture distribution, it is easy preparation aperture
Porous glass beads between 500nm~1 μm；
2, the preparation method of porous glass beads proposed by the present invention, manufacturing process is simple, and technology stability is good, obtained
The particle diameter distributions of porous glass beads, pore-size distribution and porosity it is controlled；
3, the porous glass beads of the preparation method preparation of porous glass beads proposed by the present invention, particularly useful as inhaling
Attached slow-release material is widely used in the fields such as medicine, environmental protection, the energy, building materials.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to a kind of preparation method of porous glass beads proposed according to the present invention, the porous prepared by this method
Glass microballon and its application its specific embodiment, structure, feature and its effect, detailed description is as follows.
The present invention proposes that a kind of preparation method of porous glass beads, processing step are as follows:
1) by the glass preparation substrate glass of the glass of the first acidproof level and the second acidproof level, and by the matrix
Glass is crushed, is ground up, sieved, and obtains substrate glass powder；
2) the substrate glass powder is mixed in proportion with interleaving agent, is heated to 900~1000 DEG C, heat preservation is cold
But, it is rinsed with water and removes interleaving agent, obtain glass microballoon；
3) glass microballoon is placed in acid solution and is corroded, taken out, cleaned, is filtered by vacuum, drying obtains cellular glass
Microballon.
The substrate glass is formed by two kinds of glass preparations that acid resistance differs greatly.When with acid solution clear up glass
When microballon, one such glass ingredient is cleared up by acid resolution or part, and another glass ingredient keeps original state, so that
The glass microballoon forms porous glass beads, and the preparation for changing the porous glass beads of the prior art need to be by glass
The technical process of hot split-phase sour dissolved again.By pore size, distributing homogeneity, the hole of porous glass beads prepared by hot split-phase
Rate etc. each depends on the quality of high temperature split-phase situation, and usually requires to be kept for a few houres to tens hours at a constant temperature,
Its preparation process is complicated, and technology stability is poor, while the porous pore-size of its preparation is difficult to obtain in 10nm~300nm
The porous structure of 500nm or more.The preparation method of porous glass beads proposed by the present invention is taken by preparing new substrate glass
Hot split-phase technical process when prepared by the porous beads that disappeared solves above-mentioned complex process, technology stability difference and hole ruler
Very little uncontrollable technical problem.
Preferably, the preparation method of porous glass beads above-mentioned, wherein the preparation of the substrate glass includes following
Step:
A, the glass material of the first acidproof level is crushed, is ground, sieving obtains the first glass powder of partial size≤10 μm；
B, the glass material of the second acidproof level is crushed, is ground, sieving obtains the second glass powder of partial size≤10 μm；
C, first glass powder and the second glass powder are mixed in proportion, obtains glass powder mixture；
D, the glass powder mixture is transferred in mold, in certain temperature, certain pressure and certain vacuum item
It is sintered and cooled under part to room temperature, moves back mould, obtain substrate glass.
The acid resistance of the glass material of the acidproof level of described first is poor, when being impregnated in acid solution, glass ingredient
Leaching content is big.The acidproof level of described first refers to be detected according to GB/T7962.14-2010 method, glass material it is acidproof steady
Qualitative is 4 grades or 5 grades.
The acid resistance of the glass material of the acidproof level of described second is good, when being impregnated in acid solution, glass ingredient
Leaching content is few.The acidproof level of described second refer to according to GB/T7962.14-2010 method detect, glass material it is acidproof
Stability reaches 1 grade or 2 grades.
Grinding of the present invention refers both to ball milling in the ball mill.
Preferably, the preparation method of porous glass beads above-mentioned, wherein the first glass powder and the second glass in step C
Before powder mixing, need to the first glass powder and the second glass powder be cleaned and be dried；First glass powder and second in step C
The mixed proportion of glass powder is 1:10~50 in mass.
The mixed proportion of first glass powder and the second glass powder can be adjusted according to actual needs.Improve first
The proportion of glass powder can obtain the higher porous glass beads of porosity.
Preferably, the preparation method of porous glass beads above-mentioned, wherein glass powder mixture described in step D
Sintering temperature is higher than its glass transition temperature；The vacuum degree of system is 0.1Pa~100Pa, glass powder mixture institute when sintering
The pressure received is 20~50MPa；Its sintering temperature is 800 DEG C~900 DEG C, and sintering time is 0.5~4h.
Preferably, the preparation method of porous glass beads above-mentioned, the wherein partial size of the sieve of sieving described in step 1)
Including≤30 μm, 30~50 μm, 50~100 μm, 100~200 μm, 200~300 μm, 300~400 μm and 400~500 μm.
Described its partial size of substrate glass powder is screened by using the sieve of different meshes, obtains the base of required partial size
Body glass powder, so as to adjust the size in aperture as needed, porous particle size and distribution can be according to reality
It needs to be adjusted.
Preferably, the preparation method of porous glass beads above-mentioned, wherein interleaving agent described in step 2) is selected from graphite powder
Or at least one of MgO powder；The mixed proportion of substrate glass powder and interleaving agent is 1:2~10 in mass.
The content of the interleaving agent and the particle size of Cheng Zhu are related.When interleaving agent use with it is relatively high when, then institute at
The pearl partial size of pearl is smaller.
Preferably, the preparation method of porous glass beads above-mentioned, wherein acid solution described in step 3) is selected from nitric acid, salt
At least one of acid and sulfuric acid；The concentration of the acid solution is 0.1mol/L~1mol/L；The temperature of acid solution when corrosion
It is 30 DEG C~80 DEG C, etching time is 0.5h~5h.
The concentration of the acid solution and the etching time of acid solution can adjust the size of hole to a certain extent.When
Acid solutions are appropriate, and etching time long enough, then the glass of the first acidproof level can sufficiently be cleared up, then available
Aperture is bigger, the higher porous glass beads of porosity.
Preferably, the preparation method of porous glass beads above-mentioned, wherein cleaning described in step 3) be will be through excessive erosion
Glass microballoon cleaned 2 times~5 times using deionized water, then be soaked in ethyl alcohol, propyl alcohol or isopropanol and keep 15min
~60min；It takes out and dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 0.5h~1h.
The present invention also proposes a kind of porous glass beads prepared according to method above-mentioned, the porous glass beads
It can according to need the size in adjustment aperture, porous particle size and distribution can be adjusted according to actual needs.
The present invention also proposes a kind of porous glass beads according to method above-mentioned preparation in catalyst or drug molecule
Fixed and separation field application.
The present invention is described in further detail combined with specific embodiments below.
Embodiment 1
A kind of preparation method of cellular glass, comprising the following steps:
The preparation of (1) first glass powder: 4 grades of acid-resistant stability (detecting according to GB/T7962.14-2010 method) is chosen
Borate glass, after being crushed, in a planetary ball mill, ball milling under the conditions of revolving speed 300r/min~500r/min
Then 30min~120min crosses 1500 meshes, obtains the first glass powder of partial size≤10 μm.
The preparation of (2) second glass powders: 2 grades of acid-resistant stability (detecting according to GB/T7962.14-2010 method) is chosen
Silicate glass, after being crushed, in a planetary ball mill, ball milling under the conditions of revolving speed 300r/min~500r/min
Then 30min~120min crosses 1500 meshes, obtains the second glass powder of partial size≤10 μm.
(3) glass powder mixture is prepared
By the first glass powder and the cleaning of the second glass powder, drying, according to the ratio of 1:50 in mass in batch mixer
In uniformly mix 30min, obtain glass powder mixture.
(4) it is sintered
Glass powder mixture is transferred in mold, then 800 DEG C, 40MPa pressure and vacuum degree 0.1Pa~
Under 100Pa, it is sintered 1h, after being cooled to room temperature, mould is moved back and obtains substrate glass.
(5) Cheng Zhu
Substrate glass is crushed, grinding, crosses 500 meshes, after obtaining the substrate glass powder of partial size≤30 micron, with graphite powder
Interleaving agent be uniformly mixed according to weight ratio 1:3 and is placed in corundum crucible, is heated to 900 DEG C, is kept the temperature 1h, is cooled to room temperature,
Interleaving agent is rinsed with water.
(6) corrode
The glass powder of Cheng Zhuhou is put into the nitric acid solution of 0.5mol/L, at 60 DEG C, is corroded 0.5 hour.It takes out,
With deionized water rinse 3~5 times, vacuum filtration, dry to get to partial size 30 μm or less, 30~100nm of aperture it is more
Hole glass microballoon.
Embodiment 2
The acid processing time in embodiment 1 is extended to 2 hours, available partial size is in 30 μm or less, aperture 500nm
Porous glass beads.
Embodiment 3
The preparation of (1) first glass powder: 5 grades of acid-resistant stability (detecting according to GB/T7962.14-2010 method) is chosen
Borate glass, after being crushed, in a planetary ball mill, ball milling under the conditions of revolving speed 300r/min~500r/min
Then 30min~120min crosses 1500 meshes, obtains the first glass powder of partial size≤10 μm.
The preparation of (2) second glass powders: 1 grade of acid-resistant stability (detecting according to GB/T7962.14-2010 method) is chosen
Silicate glass, after being crushed, in a planetary ball mill, ball milling under the conditions of revolving speed 300r/min~500r/min
Then 30min~120min crosses 1500 meshes, obtains the second glass powder of partial size≤10 μm.
(3) glass powder mixture is prepared
By the first glass powder and the cleaning of the second glass powder, drying, according to the ratio of 1:25 in mass in batch mixer
In uniformly mix 30min, obtain glass powder mixture.
(4) it is sintered
Glass powder mixture is transferred in mold, then in 800-900 DEG C, 20~50MPa pressure and vacuum degree
Under 0.1Pa~100Pa, it is sintered 2~4h, after being cooled to room temperature, mould is moved back and obtains substrate glass.
(5) Cheng Zhu
Substrate glass is crushed, grinding, successively crosses 140 meshes and 80 meshes, partial size can be obtained between 100~200 microns
Substrate glass powder after, be uniformly mixed being placed in corundum crucible according to weight ratio 1:5 with MgO powder interleaving agent, be heated to 900
~1000 DEG C, 1~2 hour is kept the temperature, is cooled to room temperature, rinses interleaving agent with water.
(6) corrode
The glass powder of Cheng Zhuhou is put into the hydrochloric acid solution of 0.6mol/L, at 80 DEG C, is corroded 3 hours.It takes out, uses
Deionized water rinse 3~5 times, vacuum filtration, dry to get to have partial size between 100~200 μm, aperture 200~
The porous glass beads of 500nm.
Embodiment 4
Embodiment 3 is adjusted to successively 50 meshes and 35 meshes excessively at the sieving in pearl step, adjustment corrosion acid solution is dense
Degree and etching time, available partial size is between 300~500 μm, the porous glass beads of 500~1000nm of aperture.
Further by adjusting partial size, the ratio of the first glass powder and the second glass powder, substrate glass powder is adjusted
Partial size and corrosive liquid concentration and etch process parameters, the porous glass beads of available different-grain diameter, different pore size.
" first ", " second " in technical characteristic in the claims in the present invention and/or specification etc. are each for distinguishing
Title material, and do not represent the superiority and inferiority of the performance class of each material.
Technical characteristic in the claims in the present invention and/or specification can be combined, and a combination thereof mode is not limited to weigh
The combination obtained in benefit requirement by adduction relationship.It is combined by the technical characteristic in claim and/or specification
The technical solution and protection scope of the present invention arrived.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of preparation method of porous glass beads, which is characterized in that its processing step is as follows:
1) by the glass preparation substrate glass of the glass of the first acidproof level and the second acidproof level, and by the substrate glass
It crushes, be ground up, sieved, obtain substrate glass powder；
2) the substrate glass powder is mixed in proportion with interleaving agent, is heated to 900~1000 DEG C, kept the temperature, it is cooling, it uses
Water rinsing removes interleaving agent, obtains glass microballoon；
3) glass microballoon is placed in acid solution and is corroded, taken out, cleaned, is filtered by vacuum, it is micro- to obtain cellular glass for drying
Pearl.
2. the preparation method of porous glass beads according to claim 1, which is characterized in that
The preparation of the substrate glass the following steps are included:
A, the glass material of the first acidproof level is crushed, is ground, sieving obtains the first glass powder of partial size≤10 μm；
B, the glass material of the second acidproof level is crushed, is ground, sieving obtains the second glass powder of partial size≤10 μm；
C, first glass powder and the second glass powder are mixed in proportion, obtains glass powder mixture；
D, the glass powder mixture is transferred in mold, under the conditions of certain temperature, certain pressure and certain vacuum
It is sintered and cooled to room temperature, moves back mould, obtain substrate glass.
3. the preparation method of porous glass beads according to claim 2, which is characterized in that
It, need to be clear by the first glass powder and the second glass powder before the first glass powder and the second glass powder mix in step C
It washes and dries；
The mixed proportion of the first glass powder and the second glass powder is 1:10~50 in mass in step C.
4. the preparation method of porous glass beads according to claim 2, which is characterized in that
The sintering temperature of glass powder mixture described in step D is higher than its glass transition temperature；
The vacuum degree of system is 0.1Pa~100Pa when sintering, and pressure suffered by glass powder mixture is 20~50MPa；It burns
Junction temperature is 800 DEG C~900 DEG C, and sintering time is 0.5~4h.
5. the preparation method of porous glass beads according to claim 1, which is characterized in that
The partial size of the sieve of sieving described in step 1) includes≤30 μm, 30~50 μm, 50~100 μm, 100~200 μm, 200
~300 μm, 300~400 μm and 400~500 μm.
6. the preparation method of porous glass beads according to claim 1, which is characterized in that
Interleaving agent described in step 2) is selected from at least one of graphite powder or MgO powder；
The mixed proportion of substrate glass powder and interleaving agent is 1:2~10 in mass.
7. the preparation method of porous glass beads according to claim 1, which is characterized in that
Acid solution described in step 3) is selected from least one of nitric acid, hydrochloric acid and sulfuric acid；
The concentration of the acid solution is 0.1mol/L~1mol/L；The temperature of acid solution is 30 DEG C~80 DEG C when corrosion, corrosion
Time is 0.5h~5h.
8. the preparation method of porous glass beads according to claim 1, which is characterized in that
Cleaning described in step 3) is that will be cleaned 2 times~5 times through the glass microballoon of excessive erosion using deionized water, then impregnated
15min~60min is kept in ethyl alcohol, propyl alcohol or isopropanol；
It takes out and dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 0.5h~1h.
9. a kind of porous glass beads of method preparation according to any one of claims 1 to 8.
10. a kind of porous glass beads of method preparation according to any one of claims 1 to 8 are in catalyst or drug point
The fixation of son and the application of separation field.
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| CN115159818A (en) * | 2022-05-23 | 2022-10-11 | 知美新材料科技(湖北)有限公司 | Production process flow of high-temperature glass silica beads |
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