CN115448316B - Preparation method of large-aperture spherical silicon dioxide - Google Patents
Preparation method of large-aperture spherical silicon dioxide Download PDFInfo
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- CN115448316B CN115448316B CN202211153935.4A CN202211153935A CN115448316B CN 115448316 B CN115448316 B CN 115448316B CN 202211153935 A CN202211153935 A CN 202211153935A CN 115448316 B CN115448316 B CN 115448316B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 27
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 83
- 238000000576 coating method Methods 0.000 claims abstract description 83
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- 239000012798 spherical particle Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 34
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- -1 saccharide compound Chemical class 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000889 atomisation Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- 235000014633 carbohydrates Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000009690 centrifugal atomisation Methods 0.000 abstract description 11
- 239000006041 probiotic Substances 0.000 abstract description 8
- 235000018291 probiotics Nutrition 0.000 abstract description 8
- 241001465754 Metazoa Species 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000005507 spraying Methods 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000004211 gastric acid Anatomy 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/28—Silicates, e.g. perlites, zeolites or bentonites
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
-
- 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
-
- 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
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Animal Husbandry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method of large-aperture spherical silicon dioxide, and belongs to the field of preparation of silicon dioxide. The preparation method comprises the following steps: adding water and a saccharide compound into silica sol, stirring and dissolving completely, adding whisker calcium carbonate, stirring and mixing uniformly, preparing spherical particles by a centrifugal atomization drying granulator, coating the spherical particles by using the mixed solution of the silica sol and the calcium carbonate as coating liquid, soaking by acid liquor, filtering, washing by water, drying and calcining to obtain large-aperture spherical silicon dioxide with the aperture of 1-2 mu m and the diameter of 70-180 mu m, wherein the pore volume is larger than 1mL/g, and the large-aperture spherical silicon dioxide can be used as a carrier of animal probiotics.
Description
Technical Field
The invention belongs to the field of preparation of silicon dioxide, and particularly relates to a preparation method of large-aperture spherical silicon dioxide.
Background
Probiotics are important factors for gastrointestinal health of animals and even body health, are living microorganisms, and can give health and various benefits when ingested in sufficient quantity, and the use of dead bacteria is slow in effect, large in dosage and more effective than the living probiotics. When the probiotics are taken, part of the probiotics can be killed in the stomach, so that an effective carrier needs to be provided for ensuring that the probiotics effectively reach the intestinal tract. Most known bacteria have diameters between 0.4 and 2 μm and lengths between 0.5 and 10 μm, so that the pore size of the support should be greater than 0.4 μm and the length of the pore canal should be greater than 10 μm.
Application number CN96122871.7 discloses a spherical silica gel with enlarged macropores and a manufacturing method thereof, wherein the pore diameter of the spherical silica gel is 20-15000nm. The method is to disperse solid particles with the average particle diameter of 0.1-15 mu m, which are insoluble in water, into alkaline silicate solution or inorganic acid as macroporous accelerant to realize the aim of obviously increasing the pore diameter of silica gel.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of large-aperture spherical silicon dioxide. The preparation method provided by the invention is simple, low in cost, stable in performance of the obtained spherical silicon dioxide and large in particle size.
The invention aims to provide a preparation method of large-aperture spherical silicon dioxide, which comprises the following steps:
(1) Adding water and a carbohydrate into the silica sol 1, and adding whisker calcium carbonate to obtain a mixed solution after the carbohydrate is completely dissolved;
(2) Granulating the mixed solution in the step (1) to obtain spherical particles;
(3) Adding calcium carbonate into the silica sol 2, and stirring and mixing uniformly to obtain a coating liquid;
(4) Coating the spherical particles obtained in the step (2) by using the coating liquid obtained in the step (3);
(5) Soaking the spherical particles coated in the step (4) in acid liquor, separating solid from liquid to obtain a solid phase, and drying the solid phase;
(6) And (3) calcining the solid phase dried in the step (5) to obtain the large-aperture spherical silicon dioxide.
In another embodiment of the invention, the contents of the raw materials are as follows: 10-20 parts of water, 10-20 parts of saccharide compound, 150-70 parts of silica sol, 10-15 parts of whisker calcium carbonate, 5-10 parts of calcium carbonate and 290-95 parts of silica sol.
In another embodiment of the present invention, in step (1), the whisker calcium carbonate has a diameter of 1 μm to 2 μm and a length of 50 μm to 80 μm.
In another embodiment of the present invention, in step (1), the saccharide compound is selected from one or more of glucose, sucrose, fructose, water-soluble starch.
In another embodiment of the present invention, in step (2), the granulation is performed using a centrifugal atomizing and drying granulator; wherein the rotating speed of the atomizing disk is 200rpm-300rpm, the air inlet temperature is 300-360 ℃, and the air outlet temperature is 110-120 ℃.
In another embodiment of the present invention, in step (2), the spherical particles have a particle size of 50 μm to 150 μm.
In another embodiment of the present invention, in step (3), the calcium carbonate is spherical and has an average particle diameter of 10 μm.
In another embodiment of the present invention, in step (4), coating is performed using a fluidized bed coater; wherein the air inlet temperature is 100-130 ℃, the material temperature is 60-80 ℃, the feeding speed of the coating liquid is 10-20 rpm, the stirring speed of the coating liquid is 100-500 rpm during feeding, and the spray atomization pressure is 0.1-0.3 Mpa.
In another embodiment of the present invention, in step (4), the coated spherical particles have a particle size of 70 μm to 180 μm.
In another embodiment of the present invention, in step (5), the acid is selected from one or more of hydrochloric acid, phosphoric acid, oxalic acid and nitric acid.
In another embodiment of the present invention, in the step (5), the pH of the acid solution is 1-3, and the pH of the filtrate after solid-liquid separation is 5-8.
In another embodiment of the present invention, in step (5), the soaking time is 1h to 10h.
In another embodiment of the present invention, in step (6), the calcining conditions: calcining at 600-800 deg.c for 3-6 hr.
In another embodiment of the invention, the large pore diameter spherical silica has a pore diameter of 1 μm to 2 μm, a particle diameter of 70 μm to 180 μm, and a pore volume of more than 1mL/g.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention aims to prepare spherical silicon powder which can be used as animal probiotics carrier, and the probiotics wrapped in the spherical silicon powder can pass through stomach without being destroyed by gastric acid by controlling a blocking agent, so that the spherical silicon powder can reach intestinal tracts to release in a slow and directional manner, and volatilize to regulate intestinal flora.
The invention has the advantages that the silica sol is coated with whisker calcium carbonate during granulation, and then the mixture is placed in acid liquor for soaking, and the whisker calcium carbonate is removed, so that a pore canal is formed in the silica sphere; sugar compounds are added during granulation, and then the high-temperature calcination is carried out to remove the sugar compounds, so that the pore volume of the silicon spheres is increased; the silicon spheres obtained by granulation are coated by a fluidized bed coating machine, so that the strength of the silicon spheres is improved, and the silicon spheres are not easy to break. Spherical calcium carbonate with the average particle diameter of 10 mu m is added into the coating liquid, so that the blocking of pore channels during coating can be prevented.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1
(1) Adding 10kg of water into 55kg of silica sol, stirring uniformly, adding 20kg of sucrose, stirring and dissolving completely, adding 15kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) And (3) pumping the solution obtained in the step (1) into a centrifugal atomization drying granulator for granulation, wherein the rotating speed of an atomization disc is 200rpm, the air inlet temperature is 330 ℃, the air outlet temperature is 112 ℃, and the spherical particle size is 80-150 mu m.
(3) 0.5kg of calcium carbonate is added into 9.5kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to be 110 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 10rpm, the atomization pressure is 0.1Mpa, the coating time is 2h, and the particle size after coating is 100-180 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 1.5 to be soaked for 3 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 5.6, and put into a 105 ℃ oven to be dried for 3 hours.
(6) Calcining the spherical particles in the step (5) at 600 ℃ for 4 hours to obtain spherical silicon dioxide with an average pore diameter of 1.8 mu m and a diameter of 100-180 mu m and a pore volume of 1.5mL/g.
Example 2
(1) Adding 15kg of water into 60kg of silica sol, stirring uniformly, adding 15kg of glucose, stirring completely, adding 10kg of whisker calcium carbonate with the diameter of 1-2 mu m and the length of 50-80 mu m, stirring uniformly, and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 250rpm, the air inlet temperature is 330 ℃, the air outlet temperature is 110 ℃, and the spherical particle size is 60-130 mu m.
(3) 0.5kg of calcium carbonate is added into 9.5kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a fluidized bed coating machine, setting the air inlet temperature to be 110 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 10rpm, the atomization pressure is 0.1Mpa, the coating time is 2h, and the particle size after coating is 80-160 mu m.
(5) The coated spherical particles are put into a nitric acid solution with the pH value of 2 to be soaked for 4 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.0, and put into a drying oven with the temperature of 105 ℃ to be dried for 3 hours.
(6) Calcining the spherical particles in the step (5) at 600 ℃ for 4 hours to obtain spherical silicon dioxide with an average pore diameter of 1.4 mu m and a diameter of 80-160 mu m and a pore volume of 1.4mL/g.
Example 3
(1) Adding 15kg of water into 60kg of silica sol, stirring uniformly, adding 15kg of water-soluble starch, stirring completely, adding 10kg of whisker calcium carbonate with the diameter of 1-2 mu m and the length of 50-80 mu m, stirring uniformly, and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 250rpm, the air inlet temperature is 330 ℃, the air outlet temperature is 115 ℃, and the spherical particle size is 60-130 mu m.
(3) 0.5kg of calcium carbonate is added into 9.5kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to be 110 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 15rpm, the atomization pressure is 0.2Mpa, the coating time is 2h, and the particle size after coating is 85-170 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 2.4 for soaking for 6 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.3, and put into a baking oven with the temperature of 110 ℃ for drying for 3 hours.
(6) Calcining the spherical particles in the step (5) at 600 ℃ for 4 hours to obtain spherical silicon dioxide with an average pore diameter of 1.4 mu m and a diameter of 85-170 mu m and a pore volume of 1.4mL/g.
Example 4
(1) Adding 20kg of water into 55kg of silica sol, stirring uniformly, adding 15kg of sucrose, stirring and dissolving completely, adding 10kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 300rpm, the air inlet temperature is 340 ℃, the air outlet temperature is 114 ℃, and the spherical particle size is 50-110 mu m.
(3) 0.7kg of calcium carbonate is added into 9.3kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to 120 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 17rpm, the atomization pressure is 0.2Mpa, the coating time is 1.5h, and the particle size after coating is 75-150 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 2.8 for soaking for 8 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.6, and put into a 105 ℃ oven for drying for 4 hours.
(6) Calcining the spherical particles in the step (5) at 700 ℃ for 5 hours to obtain spherical silicon dioxide with an average pore diameter of 1.5 mu m and a diameter of 75-150 mu m and a pore volume of 1.3mL/g.
Example 5
(1) Adding 20kg of water into 60kg of silica sol, stirring uniformly, adding 10kg of sucrose, stirring and dissolving completely, adding 10kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotation speed of an atomization plate is 230rpm, the air inlet temperature is 300 ℃, the air outlet temperature is 110 ℃, and the spherical particle size is 70-140 mu m.
(3) 0.6kg of calcium carbonate is added into 9.4kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to be 130 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 14rpm, the atomization pressure is 0.15Mpa, the coating time is 1.0h, and the particle size after coating is 85-165 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 1.2 for soaking for 2 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 5.4, and put into a drying oven with the temperature of 105 ℃ for drying for 3 hours.
(6) Calcining the spherical particles in the step (5) at 800 ℃ for 3 hours to obtain spherical silicon dioxide with an average pore diameter of 1.6 mu m and a diameter of 85-165 mu m and a pore volume of 1.2mL/g.
Example 6
(1) Adding 18kg of water into 57kg of silica sol, stirring uniformly, adding 12kg of sucrose, stirring and dissolving completely, adding 13kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 220rpm, the air inlet temperature is 320 ℃, the air outlet temperature is 110 ℃, and the spherical particle size is 65-140 mu m.
(3) 0.8kg of calcium carbonate is added into 9.2kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to be 100 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 12rpm, the atomization pressure is 0.12Mpa, the coating time is 1.2h, and the particle size after coating is 80-160 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 2.5 for soaking for 5 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.4, and put into a 105 ℃ oven for drying for 5 hours.
(6) Calcining the spherical particles in the step (5) at 650 ℃ for 6 hours to obtain spherical silicon dioxide with an average pore diameter of 1.6 mu m and a diameter of 80-160 mu m and a pore volume of 1.3mL/g.
Example 7
(1) Adding 12kg of water into 68kg of silica sol, stirring uniformly, adding 10kg of sucrose, stirring and dissolving completely, adding 10kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 280rpm, the air inlet temperature is 350 ℃, the air outlet temperature is 116 ℃, and the spherical particle size is 55-110 mu m.
(3) 1.0kg of calcium carbonate is added into 9.0kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to 115 ℃ and the material temperature to 63 ℃, spraying coating liquid in the step (3) by adopting a side spraying process, coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 18rpm, the atomization pressure is 0.15Mpa, the coating time is 1.6h, and the particle size after coating is 70-130 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 1.1 to be soaked for 1h, washed by a plate-and-frame filter press until the pH value of the filtrate is 5.7, and put into a 105 ℃ oven to be dried for 4 h.
(6) Calcining the spherical particles in the step (5) at 600 ℃ for 3 hours to obtain spherical silicon dioxide with an average pore diameter of 1.6 mu m and a diameter of 70-130 mu m and a pore volume of 1.1mL/g.
Comparative example 1 (comparison with example 4), the difference being that no whisker calcium carbonate was added in step (1)
(1) 20kg of water is added into 55kg of silica sol and stirred uniformly, 15kg of sucrose is added, and stirring and dissolution are complete, and stirring and mixing are uniform.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 300rpm, the air inlet temperature is 340 ℃, the air outlet temperature is 114 ℃, and the spherical particle size is 50-100 mu m.
(3) 0.7kg of calcium carbonate is added into 9.3kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) And (3) putting 1kg of spherical particles in the step (2) into a material bin of a fluidized bed coating machine, setting the air inlet temperature to 120 ℃, adopting a side spraying process to spray coating liquid in the step (3), coating the spherical particles, wherein the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 17rpm, the atomization pressure is 0.2Mpa, the coating time is 1.5h, and the particle size after coating is 75-140 mu m.
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 2.8 for soaking for 8 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.6, and put into a 105 ℃ oven for drying for 4 hours.
(6) Calcining the spherical particles in the step (5) at 700 ℃ for 5 hours to obtain the spherical silicon dioxide with the average pore diameter of 40nm, the diameter of 75-140 mu m and the pore volume of 0.6mL/g.
Comparative example 2 (in contrast to example 2), the difference being that no glucose was added in step (1)
(1) 15kg of water is added into 60kg of silica sol and stirred uniformly, 10kg of whisker calcium carbonate with the diameter of 1-2 mu m and the length of 50-80 mu m is added, and the mixture is stirred uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 250rpm, the air inlet temperature is 330 ℃, the air outlet temperature is 110 ℃, and the spherical particle size is 60-120 mu m.
(3) 0.5kg of calcium carbonate is added into 9.5kg of silica sol, and the mixture is stirred and mixed uniformly to prepare the coating liquid.
(4) 1kg of spherical particles in the step (2) is put into a material bin of a fluidized bed coating machine, the air inlet temperature is set to be 110 ℃, the material temperature is set to be 60 ℃, the coating liquid in the step (3) is sprayed by adopting a side spraying process, the spherical particles are coated, the stirring speed of the coating liquid is 200rpm, the feeding speed of the coating liquid through a diaphragm pump is 10rpm, the atomization pressure is 0.1Mpa, the coating time is 2h, and the particle size after coating is 80-150 mu m
(5) The coated spherical particles are put into hydrochloric acid solution with the pH value of 2 to be soaked for 4 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 6.0, and put into a drying oven with the temperature of 105 ℃ to be dried for 3 hours.
(6) Calcining the spherical particles in the step (5) at 600 ℃ for 4 hours to obtain spherical silicon dioxide with the pore diameter of 1.4 mu m and the diameter of 80-150 mu m and the pore volume of 0.4mL/g.
Comparative example 3 (comparison with example 1), except that step (3) was not present, i.e., coating with coating solution was not carried out
(1) Adding 10kg of water into 55kg of silica sol, stirring uniformly, adding 20kg of sucrose, stirring and dissolving completely, adding 15kg of whisker calcium carbonate with the diameter of 1-2 μm and the length of 50-80 μm, stirring and mixing uniformly.
(2) Granulating the solution in the step (1) by using a centrifugal atomization drying granulator, wherein the rotating speed of an atomization disc is 200rpm, the air inlet temperature is 330 ℃, the air outlet temperature is 112 ℃, and the spherical particle size is 80-150 mu m.
(3) The spherical particles are put into hydrochloric acid solution with the pH value of 1.5 to be soaked for 3 hours, washed by a plate-and-frame filter press until the pH value of the filtrate is 5.6, and put into an oven with the temperature of 105 ℃ to be dried for 3 hours.
(4) Calcining the spherical particles in the step (3) at 600 ℃ for 4 hours to obtain the silica with the pore diameter of 1.4 mu m and the diameter of 40-120 mu m and the pore volume of 0.6mL/g.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (8)
1. The preparation method of the large-aperture spherical silicon dioxide is characterized by comprising the following steps of:
(1) Adding water and a carbohydrate into the silica sol I, and adding whisker calcium carbonate to obtain a mixed solution after the carbohydrate is completely dissolved;
(2) Granulating the mixed solution in the step (1) to obtain spherical particles;
(3) Adding calcium carbonate into the silica sol II, and stirring and mixing uniformly to obtain coating liquid;
(4) Coating the spherical particles obtained in the step (2) by using the coating liquid obtained in the step (3);
(5) Soaking the spherical particles coated in the step (4) in acid liquor, separating solid from liquid to obtain a solid phase, and drying the solid phase;
(6) Calcining the solid phase dried in the step (5) to obtain the large-aperture spherical silicon dioxide;
in the step (1), the diameter of the whisker calcium carbonate is 1-2 mu m, and the length is 50-80 mu m;
the saccharide compound is selected from one or more of glucose, sucrose, fructose and water-soluble starch.
2. The preparation method according to claim 1, wherein the contents of the raw materials are as follows: 10-20 parts of water, 10-20 parts of saccharide compound, 50-70 parts of silica sol, 10-15 parts of whisker calcium carbonate, 5-10 parts of calcium carbonate and 90-95 parts of silica sol, wherein the weight parts are counted.
3. The method according to claim 1, wherein in the step (2), the granulation is performed by using a centrifugal atomizing dryer; wherein the rotating speed of the atomizing disk is 200rpm-300rpm, the air inlet temperature is 300-360 ℃, and the air outlet temperature is 110-120 ℃.
4. The method according to claim 1, wherein in the step (4), coating is performed using a fluidized bed coater; wherein the air inlet temperature is 100-130 ℃, the material temperature is 60-80 ℃, the feeding speed of the coating liquid is 10-20 rpm, the stirring speed of the coating liquid is 100-500 rpm during feeding, and the spray atomization pressure is 0.1-0.3 Mpa.
5. The method according to claim 1, wherein in the step (4), the coated spherical particles have a particle diameter of 70 μm to 180. Mu.m.
6. The method according to claim 1, wherein in the step (5), the acid is one or more selected from the group consisting of hydrochloric acid, phosphoric acid, oxalic acid and nitric acid.
7. The method according to claim 1, wherein in step (6), the calcining conditions are: calcining at 600-800 deg.c for 3-6 hr.
8. The method according to claim 1, wherein the large pore diameter spherical silica has a pore diameter of 1 μm to 2 μm, a particle diameter of 70 μm to 180 μm, and a pore volume of more than 1mL/g.
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| JPH09110413A (en) * | 1995-10-24 | 1997-04-28 | Mizusawa Ind Chem Ltd | Spherical silica gel having increased macropore and its production |
| CN101890376A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium-silicon composite oxide carrier and preparation method thereof |
| CN104938791A (en) * | 2015-06-11 | 2015-09-30 | 深圳市裕农科技股份有限公司 | Fodder baking soda stomach-pass sustained-release agent and preparation method thereof |
| CN105396569A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
| CN110813285A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical surface-surrounded mesoporous material silica gel composite material as carrier and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09110413A (en) * | 1995-10-24 | 1997-04-28 | Mizusawa Ind Chem Ltd | Spherical silica gel having increased macropore and its production |
| CN101890376A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium-silicon composite oxide carrier and preparation method thereof |
| CN104938791A (en) * | 2015-06-11 | 2015-09-30 | 深圳市裕农科技股份有限公司 | Fodder baking soda stomach-pass sustained-release agent and preparation method thereof |
| CN105396569A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
| CN110813285A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical surface-surrounded mesoporous material silica gel composite material as carrier and preparation method and application thereof |
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