CN116216725A - Treatment method for adjusting aperture, specific surface area and pore volume of silica microsphere - Google Patents
Treatment method for adjusting aperture, specific surface area and pore volume of silica microsphere Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 177
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000004005 microsphere Substances 0.000 title claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 33
- 229910052753 mercury Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 3
- 241000411851 herbal medicine Species 0.000 abstract description 2
- 102000039446 nucleic acids Human genes 0.000 abstract description 2
- 108020004707 nucleic acids Proteins 0.000 abstract description 2
- 150000007523 nucleic acids Chemical class 0.000 abstract description 2
- 239000002773 nucleotide Substances 0.000 abstract description 2
- 125000003729 nucleotide group Chemical group 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 238000002791 soaking Methods 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- C01P2006/14—Pore volume
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- 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
- C01P2006/16—Pore diameter
Abstract
The invention discloses a treatment method for adjusting the pore diameter, specific surface area and pore volume of silica microspheres, which is used for treating silica microspheres with average volume particle diameter of about 50um, pore diameter (P.D.) of 100nm, specific surface area (S.A.) of 30 square meters per gram and pore volume (P.V.) of 0.56ml/g, so that the pore diameter, pore volume and specific surface area are greatly increased, the absorption capacity of the pores of the silica microspheres on natural effective components such as protein, sugar, nucleotide, nucleic acid and Chinese herbal medicine is improved, the separation capacity of the silica microspheres is improved, and the silica microspheres are applied to separation fillers in more fields. The prior method for increasing the aperture, pore volume and specific surface area of the silicon dioxide microspheres mainly comprises alkali etching, hydrofluoric acid etching, high-temperature heating treatment after phosphoric acid soaking, and drying and calcining treatment after sodium chloride soaking.
Description
Technical Field
The invention relates to the technical field of silica microspheres, in particular to a treatment method for adjusting the pore diameter, specific surface area and pore volume of a silica microsphere.
Background
One determinant of the efficiency of silica microspheres in separating target materials is the size of the microsphere pore size, which limits how large the microspheres can separate target materials and the separation efficiency. The separation of the effective components in protein, antibody medicine, saccharide, nucleic acid, nucleotide, natural matter and Chinese herbal medicine needs large pore size microballoon. Reaming of silica microspheres is thus an effective means of increasing microsphere size. Large pore size microspheres are used for separation, purification, analysis, catalyst carriers, drug carriers, and the like.
The large-aperture microspheres improve the diffusion speed, the separation flow speed and the separation efficiency of target substances, and are expected to realize industrialization and mass production of the separation device. Based on the four modes for increasing the particle size of the silica microspheres, hydrofluoric acid firstly eliminates the adverse effects on the environment and the human health, and two modes of phosphoric acid and salt adding calcination have large heat energy requirements and deviate from the energy saving and emission reduction policies, so that the alkali etching mode is selected to increase the pore size, pore volume and specific surface area of the silica microspheres, and the morphology of the microspheres is kept unchanged.
Based on the above, the invention designs a treatment method for adjusting the aperture, specific surface area and pore volume of the silica microsphere to solve the above problems.
Disclosure of Invention
In order to solve the problems, the invention provides the following technical scheme:
a treatment method for adjusting the aperture, specific surface area and pore volume of a silicon dioxide microsphere comprises the following steps: the pore volume (p.v.) and the specific surface area s.a.) are increased while the microsphere pore diameter (p.d.) is increased, or the pore volume and the specific surface area are increased while the microsphere pore diameter is increased or the pore diameter is maintained unchanged. The pore diameter, pore volume and specific surface area of the microspheres were measured by mercury intrusion.
S1, silicon dioxide can be dissolved in high-concentration alkali liquor, in order to keep the integrity of the microsphere, the concentration of sodium hydroxide is preferably lower than 2mol/l, the concentration of sodium hydroxide is 0.01-2 mol/l, and the concentration of sodium hydroxide is preferably 0.1-1 mol/l.
S2, uneven dissolution occurs on the outer surface of the silica particles, irregularities are formed on the surface, the specific surface area increases, and similarly, the pore diameter increases and the pore volume increases because the wall surface inside the pores dissolves in contact with the alkali solution that intrudes into the pores.
S3, after alkali dissolution, pH=1-3 is adjusted by acid for 0.1-2 hours, and then washing, filtering and drying are started. After alkali treatment, the aperture of the microsphere is increased by 0.5-50%, the pore volume is increased by 0.2-5 times, and the specific surface area is increased by 0.1-4 times.
S4, the concentration of sodium hydroxide is 0.01-2 mol/l, and most preferably 0.1-1 mol/l. When the alkali solution concentration is insufficient, the amount of the silicon dioxide dissolved by the pores is too small, the pore diameter is not changed so much, and when the alkali solution concentration is too high, the microsphere appearance is likely to be severely corroded, or the microspheres are partially dissolved, so that the microspheres are crushed. The most preferential alkali solution dissolution time is 1-20 hours. The dissolution temperature is 5-80 ℃, preferably 20-50 ℃.
S5, the silicon dioxide microsphere requires pore diameter of 30-3500 nm (preferably 50-1000 nm), pore volume: 0.5-3 ml/g, specific surface area: 15' -2000 square meters per gram. The microsphere used in the patent is a large-aperture silicon dioxide microsphere prepared by the company after emulsification. The average volume particle diameter of the microsphere is 50um, the pore diameter is about 100nm, the pore volume is 0.56ml/g, and the specific surface area is 30 square meters/g.
Further, the mercury method is operated as follows: the mercury intrusion method can measure the pore size and the pore volume of the porous material, thereby calculating the pore size distribution and the specific surface area. It is based on mercury being non-wettable to the solid surface, mercury being able to squeeze into the pores of the porous material only under the effect of pressure, the smaller the pore size the greater the pressure required.
Further, assuming that the porous material is composed of cylindrical capillaries of different sizes, according to the principle of liquid lifting in the capillaries, the relationship between the pressure P of mercury and the capillary radius r is: r=2σcos θ/P, the surface tension of mercury and the wetting angle of mercury are known, the corresponding pore size can be found from the applied pressure P, the amount of mercury intrusion can be found as the pore volume of the corresponding size, and the total pore volume and pore size distribution can be found from the volume of mercury intrusion into the porous material at a series of different pressures.
Still further, the surface area of the pores is related to the pressure required to fill all the space of the corresponding pore with mercury as: s=pΔvcosθ/σ, and the specific surface area can be estimated from the pore diameter, the applied pressure, the pore volume, and the like.
Further, the comparative operation of the properties of the silica microspheres after sodium hydroxide treatment was as follows:
(1) Alkali treatment of 0.05mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.05mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.1um, a pore diameter (p.d.) of 99.8nm, a specific surface area (s.a.) of 30.2 square meters per gram, and a pore volume (p.v.) of 0.56ml/g, were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) was 100.2nm, specific surface area (S.A.) was 32 square meters per gram, pore volume (P.V.) was 0.58ml/g, and average volume particle was 50.78. Mu.m.
(2) Alkali treatment of 0.1mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 49.62um, a pore diameter (p.d.) of 100.2nm, a specific surface area (s.a.) of 30.1 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) of 106nm, specific surface area (S.A.) of 37 square meters per gram, pore volume (P.V.) of 0.9ml/g, and average volume particle of 50.10um.
(3) Alkali treatment of 0.5mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.5mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.35um, a pore diameter (p.d.) of 101nm, a specific surface area (s.a.) of 29.5 square meters/g, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 122nm, specific surface area (S.A.) was 54.5 square meters/g, pore volume (P.V.) was 1.2ml/g, and average volume particle diameter was 49.63. Mu.m.
(4) 1mol/l alkali treatment
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then subjected to screening washing using a screen, the screened silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.43um, a pore diameter (p.d.) of 98.5nm, a specific surface area (s.a.) of 31.2 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 135nm, specific surface area (S.A.) was 78 square meters per gram, pore volume (P.V.) was 1.85ml/g, and volume average particle diameter was 49. Mu.m.
Wherein, the table of the change of the performance of the silica microsphere before and after the sodium hydroxide treatment is shown in figure 1.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1. the large-aperture microspheres improve the diffusion speed, the separation flow speed and the separation efficiency of target substances, are expected to realize industrialized mass production of the separation device, and on the basis of the existing four ways of increasing the particle size of the microspheres, hydrofluoric acid is not friendly to the environment and the human health, the two ways of phosphoric acid method and salt adding and calcining have large heat energy requirements and deviate from the energy saving and emission reduction policies, so that the alkali etching way is selected to increase the aperture, the pore volume and the specific surface area of the silicon dioxide microspheres, and the morphology of the microspheres is kept unchanged, so that the microspheres are more practical.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the change in properties of silica microspheres according to the present invention before and after sodium hydroxide treatment;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a technical scheme that:
a treatment method for adjusting the aperture, specific surface area and pore volume of a silicon dioxide microsphere comprises the following steps: the pore volume (p.v.) and the specific surface area s.a.) are increased while the microsphere pore diameter (p.d.) is increased, or the pore volume and the specific surface area are increased while the microsphere pore diameter is increased or the pore diameter is maintained unchanged. The pore diameter, pore volume and specific surface area of the microspheres were measured by mercury intrusion.
S1, silicon dioxide can be dissolved in high-concentration alkali liquor, in order to keep the integrity of the microsphere, the concentration of sodium hydroxide is preferably lower than 2mol/l, the concentration of sodium hydroxide is 0.01-2 mol/l, and the concentration of sodium hydroxide is preferably 0.1-1 mol/l.
S2, uneven dissolution occurs on the outer surface of the silica particles, irregularities are formed on the surface, the specific surface area increases, and similarly, the pore diameter increases and the pore volume increases because the wall surface inside the pores dissolves in contact with the alkali solution that intrudes into the pores.
S3, after alkali dissolution, pH=1-3 is adjusted by acid for 0.1-2 hours, and then washing, filtering and drying are started. After alkali treatment, the aperture of the microsphere is increased by 0.5-50%, the pore volume is increased by 0.2-5 times, and the specific surface area is increased by 0.1-4 times.
S4, the concentration of sodium hydroxide is 0.01-2 mol/l, and most preferably 0.1-1 mol/l. When the alkali solution concentration is insufficient, the amount of the silicon dioxide dissolved by the pores is too small, the pore diameter is not changed so much, and when the alkali solution concentration is too high, the microsphere appearance is likely to be severely corroded, or the microspheres are partially dissolved, so that the microspheres are crushed. The most preferential alkali solution dissolution time is 1-20 hours. The dissolution temperature is 5-80 ℃, preferably 20-50 ℃.
S5, the silicon dioxide microsphere requires pore diameter of 30-3500 nm (preferably 50-1000 nm), pore volume: 0.5-3 ml/g, specific surface area: 15' -2000 square meters per gram. The microsphere used in the patent is a large-aperture silicon dioxide microsphere prepared by the company after emulsification. The average volume particle diameter of the microsphere is 50um, the pore diameter is about 100nm, the pore volume is 0.56ml/g, and the specific surface area is 30 square meters/g.
In this example, the mercury porosimetry operation method is as follows: the mercury intrusion method can measure the pore size and the pore volume of the porous material, thereby calculating the pore size distribution and the specific surface area. It is based on mercury being non-wettable to the solid surface, mercury being able to squeeze into the pores of the porous material only under the effect of pressure, the smaller the pore size the greater the pressure required.
In this embodiment, assuming that the porous material is composed of cylindrical capillaries of different sizes, according to the principle of liquid lifting in the capillaries, the relationship between the pressure P of mercury and the capillary radius r is: r=2σcos θ/P, the surface tension of mercury and the wetting angle of mercury are known, the corresponding pore size can be found from the applied pressure P, the amount of mercury intrusion can be found as the pore volume of the corresponding size, and the total pore volume and pore size distribution can be found from the volume of mercury intrusion into the porous material at a series of different pressures.
In this example, the surface area of the pores is related to the pressure required to fill all the space of the corresponding pore with mercury as: s=pΔvcosθ/σ, and the specific surface area can be estimated from the pore diameter, the applied pressure, the pore volume, and the like.
In this example, the performance of the silica microspheres after sodium hydroxide treatment was compared as follows:
(1) Alkali treatment of 0.05mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.05mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.1um, a pore diameter (p.d.) of 99.8nm, a specific surface area (s.a.) of 30.2 square meters per gram, and a pore volume (p.v.) of 0.56ml/g, were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) was 100.2nm, specific surface area (S.A.) was 32 square meters per gram, pore volume (P.V.) was 0.58ml/g, and average volume particle was 50.78. Mu.m.
(2) Alkali treatment of 0.1mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 49.62um, a pore diameter (p.d.) of 100.2nm, a specific surface area (s.a.) of 30.1 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) of 106nm, specific surface area (S.A.) of 37 square meters per gram, pore volume (P.V.) of 0.9ml/g, and average volume particle of 50.10um.
(3) Alkali treatment of 0.5mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.5mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.35um, a pore diameter (p.d.) of 101nm, a specific surface area (s.a.) of 29.5 square meters/g, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 122nm, specific surface area (S.A.) was 54.5 square meters/g, pore volume (P.V.) was 1.2ml/g, and average volume particle diameter was 49.63. Mu.m.
(4) 1mol/l alkali treatment
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then subjected to screening washing using a screen, the screened silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.43um, a pore diameter (p.d.) of 98.5nm, a specific surface area (s.a.) of 31.2 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 135nm, specific surface area (S.A.) was 78 square meters per gram, pore volume (P.V.) was 1.85ml/g, and volume average particle diameter was 49. Mu.m.
Wherein, the table of the change of the performance of the silica microsphere before and after the sodium hydroxide treatment is shown in figure 1.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. A treatment method for adjusting the aperture, specific surface area and pore volume of a silicon dioxide microsphere comprises the following steps: the pore volume (p.v.) and the specific surface area s.a.) are increased while the microsphere pore diameter (p.d.) is increased, or the pore volume and the specific surface area are increased while the microsphere pore diameter is increased or the pore diameter is maintained unchanged. The pore diameter, pore volume and specific surface area of the microspheres were measured by mercury intrusion.
S1, silicon dioxide can be dissolved in high-concentration alkali liquor, in order to keep the integrity of the microsphere, the concentration of sodium hydroxide is preferably lower than 2mol/l, the concentration of sodium hydroxide is 0.01-2 mol/l, and the concentration of sodium hydroxide is preferably 0.1-1 mol/l.
S2, uneven dissolution occurs on the outer surface of the silica particles, irregularities are formed on the surface, the specific surface area increases, and similarly, the pore diameter increases and the pore volume increases because the wall surface inside the pores dissolves in contact with the alkali solution that intrudes into the pores.
S3, after alkali dissolution, pH=1-3 is adjusted by acid for 0.1-2 hours, and then washing, filtering and drying are started. After alkali treatment, the aperture of the microsphere is increased by 0.5-50%, the pore volume is increased by 0.2-5 times, and the specific surface area is increased by 0.1-4 times.
S4, the concentration of sodium hydroxide is 0.01-2 mol/l, and most preferably 0.1-1 mol/l. When the alkali solution concentration is insufficient, the amount of the silicon dioxide dissolved by the pores is too small, the pore diameter is not changed so much, and when the alkali solution concentration is too high, the microsphere appearance is likely to be severely corroded, or the microspheres are partially dissolved, so that the microspheres are crushed. The most preferential alkali solution dissolution time is 1-20 hours. The dissolution temperature is 5-80 ℃, preferably 20-50 ℃.
S5, the silicon dioxide microsphere requires pore diameter of 30-3500 nm (preferably 50-1000 nm), pore volume: 0.5-3 ml/g, specific surface area: 15' -2000 square meters per gram. The microsphere used in the patent is a large-aperture silicon dioxide microsphere prepared by the company after emulsification. The average volume particle diameter of the microsphere is 50um, the pore diameter is about 100nm, the pore volume is 0.56ml/g, and the specific surface area is 30 square meters/g.
2. The process of claim 1, wherein the mercury porosimetry is operated as follows: the mercury intrusion method can measure the pore size and the pore volume of the porous material, thereby calculating the pore size distribution and the specific surface area. It is based on mercury being non-wettable to the solid surface, mercury being able to squeeze into the pores of the porous material only under the effect of pressure, the smaller the pore size the greater the pressure required.
3. The method for treating silica microspheres according to claim 2, wherein the method comprises the steps of: assuming that the porous material is composed of cylindrical capillaries with different sizes, according to the principle of liquid lifting in the capillaries, the relationship between the pressure P of mercury and the radius r of the capillaries is as follows: r=2σcos θ/P, the surface tension of mercury and the wetting angle of mercury are known, the corresponding pore size can be found from the applied pressure P, the amount of mercury intrusion can be found as the pore volume of the corresponding size, and the total pore volume and pore size distribution can be found from the volume of mercury intrusion into the porous material at a series of different pressures.
4. The method for treating silica microspheres according to claim 2, wherein the method comprises the steps of: the surface area of the pores is related to the pressure required to fill all the space of the corresponding pore with mercury as: s=pΔvcosθ/σ, and the specific surface area can be estimated from the pore diameter, the applied pressure, the pore volume, and the like.
5. A method of treatment for adjusting pore size, specific surface area and pore volume of silica microspheres according to any one of claims 1-4, giving silica microspheres properties that are compared to the sodium hydroxide treatment before and after the treatment as follows:
(1) Alkali treatment of 0.05mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.05mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.1um, a pore diameter (p.d.) of 99.8nm, a specific surface area (s.a.) of 30.2 square meters per gram, and a pore volume (p.v.) of 0.56ml/g, were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) was 100.2nm, specific surface area (S.A.) was 32 square meters per gram, pore volume (P.V.) was 0.58ml/g, and average volume particle was 50.78. Mu.m.
(2) Alkali treatment of 0.1mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 49.62um, a pore diameter (p.d.) of 100.2nm, a specific surface area (s.a.) of 30.1 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and treated: pore size (P.D.) of 106nm, specific surface area (S.A.) of 37 square meters per gram, pore volume (P.V.) of 0.9ml/g, and average volume particle of 50.10um.
(3) Alkali treatment of 0.5mol/l
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 0.5mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then sieved and washed with a sieve, the sieved silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.35um, a pore diameter (p.d.) of 101nm, a specific surface area (s.a.) of 29.5 square meters/g, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 122nm, specific surface area (S.A.) was 54.5 square meters/g, pore volume (P.V.) was 1.2ml/g, and average volume particle diameter was 49.63. Mu.m.
(4) 1mol/l alkali treatment
10g of silica microspheres were weighed, 200ml of silica microspheres were dispersed in 1mol/l of an alkali solution, then stirred slowly at 30℃for 6 hours, then subjected to screening washing using a screen, the screened silica microspheres were dispersed in water, then sulfuric acid was added dropwise to adjust the pH of the aqueous solution to 3, and stirring was carried out at room temperature for 1 hour. Base ball: silica microspheres with an average volume particle diameter of 50.43um, a pore diameter (p.d.) of 98.5nm, a specific surface area (s.a.) of 31.2 square meters per gram, and a pore volume (p.v.) of 0.57ml/g were dispersed in water, washed, filtered and dried, and the treated silica microspheres: pore diameter (P.D.) was 135nm, specific surface area (S.A.) was 78 square meters per gram, pore volume (P.V.) was 1.85ml/g, and volume average particle diameter was 49. Mu.m.
Wherein, the table of the change of the performance of the silica microsphere before and after the sodium hydroxide treatment is shown in figure 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412517A (en) * | 2008-11-14 | 2009-04-22 | 华东理工大学 | Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere |
| KR20160044198A (en) * | 2014-10-15 | 2016-04-25 | 한국기초과학지원연구원 | Method for Preparing Mesoporous Silica and the Mesoporous Silica Therefrom |
| JP2020132479A (en) * | 2019-02-21 | 2020-08-31 | 三菱ケミカル株式会社 | Silica particle, silica sol, polishing composition, polishing method, method of manufacturing semiconductor wafer, and method of manufacturing semiconductor device |
| JP2021059490A (en) * | 2019-10-09 | 2021-04-15 | 日揮触媒化成株式会社 | Silica-based particle dispersion and method for producing the same |
| CN114797861A (en) * | 2022-04-25 | 2022-07-29 | 国能(山东)能源环境有限公司 | Magnetic mesoporous silica microsphere and preparation method and application thereof |
-
2023
- 2023-02-14 CN CN202310109302.1A patent/CN116216725A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412517A (en) * | 2008-11-14 | 2009-04-22 | 华东理工大学 | Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere |
| KR20160044198A (en) * | 2014-10-15 | 2016-04-25 | 한국기초과학지원연구원 | Method for Preparing Mesoporous Silica and the Mesoporous Silica Therefrom |
| JP2020132479A (en) * | 2019-02-21 | 2020-08-31 | 三菱ケミカル株式会社 | Silica particle, silica sol, polishing composition, polishing method, method of manufacturing semiconductor wafer, and method of manufacturing semiconductor device |
| JP2021059490A (en) * | 2019-10-09 | 2021-04-15 | 日揮触媒化成株式会社 | Silica-based particle dispersion and method for producing the same |
| CN114797861A (en) * | 2022-04-25 | 2022-07-29 | 国能(山东)能源环境有限公司 | Magnetic mesoporous silica microsphere and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐慧娟: "中空介孔氧化硅纳米材料的制备及其药物传输性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 February 2016 (2016-02-15), pages 015 - 133 * |
| 罗民华: "《多孔陶瓷实用技术》", 31 March 2006, 中国建材工业出版社, pages: 134 - 136 * |
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