CN104986776A - Method for preparing hollow glass beads - Google Patents
Method for preparing hollow glass beads Download PDFInfo
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- CN104986776A CN104986776A CN201510487615.6A CN201510487615A CN104986776A CN 104986776 A CN104986776 A CN 104986776A CN 201510487615 A CN201510487615 A CN 201510487615A CN 104986776 A CN104986776 A CN 104986776A
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- 239000011521 glass Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000011324 bead Substances 0.000 title abstract description 4
- 241000195493 Cryptophyta Species 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 35
- 239000011707 mineral Substances 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 13
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- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005457 optimization Methods 0.000 claims abstract description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 25
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- 239000000047 product Substances 0.000 claims description 25
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 21
- 238000012258 culturing Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 14
- 235000015097 nutrients Nutrition 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004576 sand Substances 0.000 claims description 11
- 229910052845 zircon Inorganic materials 0.000 claims description 11
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 5
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- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
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- 230000007547 defect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008188 pellet Substances 0.000 abstract 2
- 235000011194 food seasoning agent Nutrition 0.000 abstract 1
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- 210000004027 cell Anatomy 0.000 description 20
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention provides a method for preparing hollow glass beads and relates to preparation of finely dispersed silica. The method is a biological template method by which hollow silicon dioxide pellets are obtained after natural mineral materials capable of emitting far infrared rays are added to mixed liquor prepared from processed algal cells, tetraethoxysilane and base catalyst, and then stirring, seasoning, centrifuging, washing, drying and calcinating are conducted. The method specifically comprises the steps of preparation of algae, optimization of the performance of the natural mineral materials capable of emitting far infrared rays, and preparation of the hollow glass beads. The method overcomes the defects that the quality of hollow silicon dioxide pellets produced in the prior art is unstable, preparation technology is complicated, and industrial production is not facilitated.
Description
Technical field
Technical scheme of the present invention relates to the preparation of finely divided silica, specifically a kind of preparation method of hollow glass micropearl.
Background technology
Hollow beads is a kind of special spherical shell type material, its size is between nanometer is to several microns, inside is hollow structure, its quality is light, particle diameter is little, hardness is high, perfectly round degree is high, dispersed and self-extinguishing is good, and there is heat insulation, sound insulation, withstand voltage, wear-resisting, acid and alkali-resistance and the performance such as fire-resistant, have a extensive future.Existing application in the diagnosis etc. of high-selectivity catalyst or support of the catalyst, electrocatalysis, lithium cell, light filler, advanced low-k materials, controlled drug transport and slowly-releasing and disease.As a kind of special material colony, monodisperse silica hollow microsphere shape is comparatively even, microsphere diameter is less, minimumly can reach hundreds of micron, moiety is single, surface easily functionalization, has great using value in each side such as the self-assembly of photonic crystal, chromatograph packing material, light filler and refractory materialss.Simultaneously silicon dioxide hollow microballon can also be applied in preparation and has the compound of cavity package function and have the medicine aspect of slow-release function, thus also can play a role in medicine, medical treatment, artificial cell, diagnosis of disease, false proof and all many-sides of spices.
At present, the preparation of hollow microsphere becomes the focus of people's concern gradually, and the preparation method of the hollow microsphere of prior art is mainly template.The ultimate principle of template can be summed up as: with air cavity, micelle, drop or particulate as template, forms shell by the method for deposition, absorption, cohesion, self-assembly or surface reaction.The conventional method preparing Inorganic Hollow Microspheres is template, is template usedly divided into hard template and soft template two kinds.Hard template mainly contains polystyrene microsphere, inorganic silicon dioxide or calcium carbonate particles, and soft template mainly contains micro-capsule, micella, emulsion droplets or bubble.The defect of above-mentioned template is: often generate with toxic byproduct in production, uneconomical, not environmentally with dangerous.Biological template method selects microorganism to be raw material, and non-toxic by-products generates, and economy, environmental protection and safety, is a kind ofly to prepare the novel method with special construction material.At present, the method is used widely in the preparation of tiny balloon, and the natural biologicals such as general algae, pollen, bacterium and virus can be used as biological template.CN102874823A discloses with pollen granule for the homogeneous silicon dioxide hollow microsphere of biological Template preparation shape, and described processing method to be made a living thing Template preparation silicon dioxide hollow microsphere with Rose powder.First preparation process passes through the Surface coating Silica hydrogel of hydrolysis-condensation reaction at pollen granule of tetraethyl orthosilicate, then high temperature is utilized to remove template, form mesoporous silicon oxide hollow microsphere, its defect is: 1. adopt pollen as raw material, make obtained product large by the quality influence of pollen own, the stability of limits product quality; 2. need the technique such as broken wall state controlling pollen, preparation technology and need condition comparatively complicated, be unfavorable for the popularization of suitability for industrialized production and high value added product.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method providing a kind of hollow glass micropearl, that the natural minerals with the emitting far-infrared function of energy joins in the mixed solution prepared by the frustule processed, tetraethoxy and alkaline catalysts, through stirrings, ageing, centrifugal, washing, dry and calcine art breading, the biological template method of obtained hollow silica microsphere, the method overcome the silicon dioxide hollow microsphere unstable product quality that prior art is produced, complicated process of preparation, is unfavorable for the defect of suitability for industrialized production.
The present invention solves this technical problem adopted technical scheme: a kind of preparation method of hollow glass micropearl, and concrete steps are as follows:
The first step, the preparation of algae:
(1.1) algae is cultivated: the mother liquor preparing Algae culture solution by the formula of BG11 liquid nutrient medium, to this mother liquor, in the deionized water of experiment and algae seeded process, the glassware used carries out autoclave sterilization, after cooling according to the proportioning of BG11 nutrient solution, mother liquor is mixed with deionized water constant volume and is made into algae culturing liquid, algae kind being moved into is equipped with in the culturing bottle of algae culturing liquid, finally culturing bottle is put into growth cabinet to cultivate 15 ~ 20 days, culture temperature is 25 ~ 35 DEG C, intensity of illumination 1900 ~ 2100lx, light application time is 10 ~ 15h, pH value is 7.5 ~ 8.5, obtained cultivation algae algae liquid, stand-by,
(1.2) processed is carried out to algae: configuration concentration be the fixing algae reagent of 3vol.% ~ 5vol.% solution and respectively configuration concentration be the cosolvent solution for later use of 20vol.%, 40vol.%, 60vol.% and 80vol.%, draw by the obtained cultivation algae algae liquid of (1.1) step with glue head dropper, in injection centrifuge tube, centrifuge tube symmetry is put into whizzer, balance between two, carry out centrifugal with the rotating speed of 5000 ~ 7000r/min, supernatant liquor in centrifuge tube is removed after centrifugal 5 ~ 7min, repeat aforesaid operations until collect the algae sedimentation cell of 2 ~ 5mL, the concentration injecting above-mentioned configuration in the centrifuge tube leaving algae sedimentation cell is the solution that 3 ~ 5vol.% fixes algae reagent, 1 ~ 3h is left standstill after mixing, supernatant liquor is removed by after centrifugal for algae suspension liquid 5 ~ 7min, then in centrifuge tube, inject deionized water and mix, supernatant liquor is removed after recentrifuge 5 ~ 7min, repeated washing 3 times, rotating speed used is 5000 ~ 7000r/min, the concentration adding above-mentioned configuration in the centrifuge tube leaving the algae sedimentation cell after fixing is the cosolvent solution of 20vol.% and mixes, centrifugal 3 ~ 7min after dehydration 10 ~ 20min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 40vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 60vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 80vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, above-mentioned dehydration and centrifugally operated twice is repeated again with anhydrous cosolvent, obtain the algae that processed is crossed thus,
Second step, has the performance optimization process of the natural minerals of the emitting far-infrared function of energy:
The natural minerals block with the emitting far-infrared function of energy is first tentatively broken into the small-particle of diameter at 1 ~ 2mm, stand-by, in mass ratio for having the natural minerals of the emitting far-infrared function of energy: ball milling ball: cosolvent=1:3:1.5 ~ 2 are poured in ball grinder after mixing, with the rotating speed ball milling 2 ~ 3h of 1000 ~ 1200r/min, the product of this wet ball grinding is put into baking oven dry, temperature is set to 60 ~ 80 DEG C, time is 6 ~ 8h, the natural minerals with the emitting far-infrared function of energy after drying is calcined, calcining temperature is 700 ~ 900 DEG C, having after calcining can the natural minerals of emitting far-infrared function be sieved, take out granularity be 300 ~ 100 objects heat treated have can the natural minerals of emitting far-infrared function stand-by,
3rd step, the preparation of hollow glass micropearl:
(3.1) preparing base soln: 2 ~ 4mL tetraethoxy and 8 ~ 16mL cosolvent are hybridly prepared into solution A by the volume ratio of 1:4, is that the alkaline solution of 27%, 4 ~ 20mL deionized water and 3 ~ 15mL cosolvent are by volume for the ratio of 1:4:3 is hybridly prepared into B solution by 1 ~ 5mL mass percent concentration;
(3.2) hollow silica microsphere is prepared: get 8 ~ 40mL B solution that (3.1) step prepares, adding volume is wherein the algae that processed that the first step of 3mL obtains is crossed, supersound process 2 ~ 4min, ensure that frustule forms suspension in solution B, make frustule surface planar water and alkali quickly and evenly, this suspension is put on magnetic stirring apparatus and stirs, the solution A that (3.1) step prepares dropwise is added drop-wise in the suspension on agitator, to ensure the SiO formed
2colloidal particle is evenly wrapped in frustule surface, form a kind of mixed solution, the natural minerals with the emitting far-infrared function of energy that 0.2 ~ 0.4g is heat treated is added in this mixed solution, at room temperature Keep agitation 24 ~ 48h, ageing 12 ~ 36h under room temperature, with the rotating speed collected by centrifugation product of 6000r/min, and with deionized water, centrifuge washing is carried out to product, products therefrom is dried, temperature is set to 40 ~ 60 DEG C, hollow microsphere is obtained again by retort furnace calcining, during calcining, temperature rise rate is 2 ~ 4 DEG C/min, calcining temperature is 500 ~ 600 DEG C, soaking time is 7 ~ 9h, obtained hollow silica microsphere and hollow glass micropearl thus.
The preparation method of above-mentioned a kind of hollow glass micropearl, described algae is 1 ~ 3 kind in cytoalgae, chlorella or chroococcoid.
The preparation method of above-mentioned a kind of hollow glass micropearl, described fixing algae reagent is 1 ~ 3 kind in formaldehyde, acetaldehyde or phenylacrolein.
The preparation method of above-mentioned a kind of hollow glass micropearl, the described natural minerals with the emitting far-infrared function of energy is 1 ~ 5 kind in trichroite, mullite, tourmalinite, chromite or zircon sand.
The preparation method of above-mentioned a kind of hollow glass micropearl, described alkali is strong aqua, sodium hydroxide or potassium hydroxide.
The preparation method of above-mentioned a kind of hollow glass micropearl, described cosolvent is ethanol, propyl alcohol or acetone.
The preparation method of above-mentioned a kind of hollow glass micropearl, used starting material are all by commercially available, and operating procedure is that those skilled in the art know.
The invention has the beneficial effects as follows: compared with prior art, outstanding substantive distinguishing features of the present invention is:
(1) the present invention is that a kind of natural minerals with the emitting far-infrared function of energy joins by the algae processed, in the mixed solution of tetraethoxy and alkaline catalysts preparation, through stirring, ageing, centrifugal, washing, the art breading of drying and calcining, the biological template method of obtained hollow silica microsphere and hollow glass micropearl, wherein, the preparation speed of silicon dioxide hollow microsphere is improve under the effect that the natural minerals with the emitting far-infrared function of energy is emitting far-infrared, reason is: the far infrared rays that the natural minerals with the emitting far-infrared function of energy is launched can reduce the cluster of water molecules, reduce colloidal particle in mixing solutions and spread the resistance be subject to, the natural minerals with the emitting far-infrared function of energy can also improve the dispersiveness of silicon dioxide hollow microsphere, increase colloidal particle diffusion double layer thickness, increase the repulsion potential energy between colloidal particle, reduce the cluster between colloidal particle, increase the chance that colloidal particle is combined with frustule.
(2) have can the natural minerals Borate Minerals of emitting far-infrared function as a kind of, and it has some special character, such as: produce negative ion, emitting far-infrared, there is permanent electrode effect and form electrostatic field etc.For tourmalinite material, tourmalinite material is all widely used in many fields such as environment protection, HUMAN HEALTH, medication chemistry, health-care textile, electromagnetic shielding, material of construction.Tourmalinite take boracic as the ring texture silicate minerals of feature, belongs to trigonal system, have excellent spontaneous polarization performance and emitting far-infrared performance, can produce polarized electric field, activated water molecule.
At present, there are no having the bibliographical information of hollow glass micropearl that can biological template be utilized to synthesize under the natural minerals effect of emitting far-infrared function.
Compared with prior art, marked improvement of the present invention is: the present invention overcomes the silicon dioxide hollow microsphere unstable product quality that prior art template is produced, complicated process of preparation, is unfavorable for the defect of suitability for industrialized production.Hollow glass micropearl obtained by the inventive method is the heat insulating function filler of lightweight, ensures the density effectively reducing gained matrix material, thus significantly improves its heat-proof quality.
The following examples will show beneficial effect of the present invention further.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the electron scanning micrograph of the microtexture of the hollow glass micropearl that the inventive method obtains.
Embodiment
The electron scanning micrograph display of the microtexture of the hollow glass micropearl that Fig. 1 the inventive method obtains, the centre of this hollow glass micropearl is broken hollow microsphere, the microballoon wall wall thickness of this microballoon is about 0.2 μm as can be seen from Figure, is 1/10th of microsphere diameter.From this hollow glass micropearl microtexture, when taking alkali as catalyzer, microballoon wall to be interconnected close-packed arrays and being formed by Van der Waals force, hydrogen bond or chemical bond force by micelle one by one.This microsphere surface is uneven, further increases its performance that is heat insulation and absorption.
Embodiment 1
The preparation method of a kind of hollow glass micropearl of the present embodiment, concrete steps are as follows:
The first step, the preparation of cytoalgae:
(1.1) algae is cultivated: the mother liquor preparing cytoalgae nutrient solution by the formula of BG11 liquid nutrient medium, to this mother liquor, in the deionized water of experiment and cytoalgae seeded process, the glassware used carries out autoclave sterilization, after cooling according to the proportioning of BG11 nutrient solution, mother liquor is mixed with deionized water constant volume and is made into algae culturing liquid, cytoalgae algae kind being moved into is equipped with in the culturing bottle of algae culturing liquid, finally culturing bottle is put into growth cabinet and cultivate 15 days, culture temperature is 35 DEG C, intensity of illumination 1900lx, light application time is 15h, pH value is 7.5, obtained cultivation algae algae liquid is cytoalgae algae liquid, stand-by,
(1.2) processed is carried out to algae:: configuration concentration be the fixing algae reagent of 3vol.% formaldehyde solution and respectively configuration concentration be that the cosolvent ethanolic soln of 20vol.%, 40vol.%, 60vol.% and 80vol.% is stand-by, draw by the obtained cytoalgae algae liquid of (1.1) step with glue head dropper, in injection centrifuge tube, centrifuge tube symmetry is put into whizzer, balance between two, carry out centrifugal with the rotating speed of 5000r/min, supernatant liquor in centrifuge tube is removed after centrifugal 7min, repeat aforesaid operations until collect the cytoalgae sedimentation cell of 3mL, the concentration injecting above-mentioned configuration in the centrifuge tube leaving cytoalgae sedimentation cell is the formaldehyde solution that 3vol.% fixes algae reagent, 1h is left standstill after mixing, supernatant liquor is removed by after the centrifugal 5min of cytoalgae sedimentation cell after fixing, then in centrifuge tube, inject deionized water and mix, supernatant liquor is removed after recentrifuge 5min, repeated washing 3 times, rotating speed used is 7000r/min, the concentration adding above-mentioned configuration in the centrifuge tube leaving the cytoalgae sedimentation cell after fixing is the cosolvent ethanolic soln of 20vol.% and mixes, centrifugal 7min after dehydration 10min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent ethanolic soln of 40vol.% and mixes, centrifugal 7min after dehydration 12min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent ethanolic soln of 60vol.% and mixes, centrifugal 7min after dehydration 12min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent ethanolic soln of 80vol.% and mixes, centrifugal 7min after dehydration 12min, above-mentioned dehydration and centrifugally operated twice is repeated again with anhydrous cosolvent ethanol, obtain the cytoalgae that processed is crossed thus,
Second step, has the performance optimization process of the natural minerals of the emitting far-infrared function of energy:
The electric stone of natural minerals with the emitting far-infrared function of energy is first tentatively broken into the small-particle of diameter at 1mm, stand-by, be tourmalinite in mass ratio: ball milling ball: pour in ball grinder after cosolvent ethanol=1:3:1.5 mixing, with the rotating speed ball milling 3h of 1000r/min, the product of this wet ball grinding is put into baking oven dry, temperature is set to 60 DEG C, and the time is 8h, calcined by tourmalinite after drying, calcining temperature is 700 DEG C; Tourmalinite after calcining is sieved, take out granularity be 300 ~ 100 objects heat treated have can the natural minerals tourmalinite of emitting far-infrared function stand-by;
3rd step, the preparation of hollow glass micropearl:
(3.1) preparing base soln: 2mL tetraethoxy and 8mL cosolvent ethanol are hybridly prepared into solution A by the volume ratio of 1:4, is that the ammonia soln of 27%, 4mL deionized water and 3mL cosolvent ethanol are by volume for the ratio of 1:4:3 is hybridly prepared into B solution by 1mL mass percent concentration;
(3.2) hollow silica microsphere is prepared: get the 8mL B solution that (3.1) step prepares, adding volume is wherein the cytoalgae that processed that the first step of 3mL obtains is crossed, supersound process 2min, ensure that frustule forms suspension in solution B, make cell surface planar water and alkali quickly and evenly, this suspension is put on magnetic stirring apparatus and stirs, the solution A that (3.1) step prepares dropwise is added drop-wise in the suspension on agitator, to ensure the SiO formed
2colloidal particle is evenly wrapped in cytoalgae frustule surface, form a kind of mixed solution, the tourmalinite that 0.2g is heat treated is added in this mixed solution, at room temperature Keep agitation 24h, ageing 36h under room temperature, with the rotating speed collected by centrifugation product of 6000r/min, and with deionized water, centrifuge washing is carried out to product, products therefrom is dried, temperature is set to 40 DEG C, hollow microsphere is obtained again by retort furnace calcining, during calcining, temperature rise rate is 2 DEG C/min, calcining temperature is 500 DEG C, soaking time is 9h, obtained hollow silica microsphere and hollow glass micropearl thus.
Embodiment 2
The preparation method of a kind of hollow glass micropearl of the present embodiment, concrete steps are as follows:
The first step, the preparation of chlorella:
(1.1) algae is cultivated: the mother liquor preparing chlorella nutrient solution by the formula of BG11 liquid nutrient medium, to this mother liquor, in the deionized water of experiment and chlorella seeded process, the glassware used carries out autoclave sterilization, after cooling according to the proportioning of BG11 nutrient solution, mother liquor is mixed with deionized water constant volume and is made into algae culturing liquid, chlorella algae kind being moved into is equipped with in the culturing bottle of algae culturing liquid, finally culturing bottle is put into growth cabinet and cultivate 17 days, culture temperature is 30 DEG C, intensity of illumination 2000lx, light application time is 13h, pH value is 8, obtained cultivation algae algae liquid is chlorella algae liquid, stand-by,
(1.2) processed is carried out to algae:: configuration concentration be the fixing algae reagent of 4vol.% acetaldehyde solution and respectively configuration concentration be that the cosolvent propanol solution of 20vol.%, 40vol.%, 60vol.% and 80vol.% is stand-by, the chlorella algae liquid after the cultivation obtained by (1.1) step is drawn with glue head dropper, in injection centrifuge tube, centrifuge tube symmetry is put into whizzer, balance between two, carry out centrifugal with the rotating speed of 6000r/min, remove supernatant liquor in centrifuge tube after centrifugal 6min and repeat aforesaid operations until collect the chlorella sedimentation cell of 4mL, the concentration injecting above-mentioned configuration in the centrifuge tube leaving chlorella sedimentation cell is the acetaldehyde solution that 4vol.% fixes algae reagent, 2h is left standstill after mixing, supernatant liquor is removed by after the centrifugal 6min of chlorella sedimentation cell after fixing, then in centrifuge tube, inject deionized water and mix, supernatant liquor is removed after recentrifuge 6min, repeated washing 3 times, rotating speed used is 6000r/min, the concentration adding above-mentioned configuration in the centrifuge tube leaving the chlorella sedimentation cell after fixing is the cosolvent propanol solution of 20vol.% and mixes, centrifugal 4min after dehydration 15min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent propanol solution of 40vol.% and mixes, centrifugal 4min after dehydration 14min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent propanol solution of 60vol.% and mixes, centrifugal 4min after dehydration 15min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent propanol solution of 80vol.% and mixes, centrifugal 4min after dehydration 15min, above-mentioned dehydration and centrifugally operated twice is repeated again with anhydrous cosolvent propyl alcohol, obtain the chlorella that processed is crossed thus,
Second step, has the performance optimization process of the natural minerals of the emitting far-infrared function of energy:
The natural minerals trichroite block with the emitting far-infrared function of energy is first tentatively broken into the small-particle of diameter at 1.5mm, stand-by, be trichroite in mass ratio: ball milling ball: pour in ball grinder after cosolvent propyl alcohol=1:3:1.8 mixing, with the rotating speed ball milling 2.5h of 1100r/min, the product of this wet ball grinding is put into baking oven dry, temperature is set to 70 DEG C, and the time is 7h, calcined by trichroite after drying, calcining temperature is 800 DEG C; Trichroite after calcining is sieved, take out granularity be 300 ~ 100 objects heat treated have can the natural minerals trichroite of emitting far-infrared function stand-by;
3rd step, the preparation of hollow glass micropearl:
(3.1) preparing base soln: 3mL tetraethoxy and 12mL cosolvent propyl alcohol are hybridly prepared into solution A by the volume ratio of 1:4, is that the sodium hydroxide solution of 27%, 10mL deionized water and 7.5mL cosolvent propyl alcohol are by volume for the ratio of 1:4:3 is hybridly prepared into B solution by 2.5mL mass percent concentration;
(3.2) hollow silica microsphere is prepared: get the 20mL B solution that (3.1) step prepares, adding volume is wherein the chlorella that processed that the first step of 3mL obtains is crossed, supersound process 3min, ensure that chlorella cells forms suspension in solution B, make chlorella algae cell surface planar water and alkali quickly and evenly, this suspension is put on magnetic stirring apparatus and stirs, the solution A that (3.1) step prepares is added drop-wise in the suspension on agitator, to ensure the SiO formed
2colloidal particle is evenly wrapped in chlorella algae cell surface, form a kind of mixed solution, the trichroite that 0.3g is heat treated is added in this mixed solution, at room temperature Keep agitation 36h, ageing 24h under room temperature, with the rotating speed collected by centrifugation product of 6000r/min, and with deionized water, centrifuge washing is carried out to product, products therefrom is dried, temperature is set to 50 DEG C, hollow microsphere is obtained again by retort furnace calcining, during calcining, temperature rise rate is 3 DEG C/min, calcining temperature is 550 DEG C, soaking time is 8h, obtained hollow silica microsphere and hollow glass micropearl thus.
Embodiment 3
The preparation method of a kind of hollow glass micropearl of the present embodiment, concrete steps are as follows:
The first step, the preparation of chroococcoid:
(1.1) algae is cultivated: the mother liquor preparing chroococcoid nutrient solution by the formula of BG11 liquid nutrient medium, to this mother liquor, in the deionized water of experiment and chroococcoid seeded process, the glassware used carries out autoclave sterilization, after cooling according to the proportioning of BG11 nutrient solution, mother liquor is mixed with deionized water constant volume and is made into algae culturing liquid, chroococcoid algae kind being moved into is equipped with in the culturing bottle of algae culturing liquid, finally culturing bottle is put into growth cabinet and cultivate 20 days, culture temperature is 25 DEG C, intensity of illumination 2100lx, light application time is 10h, pH value is 8.5, obtained cultivation algae algae liquid is chroococcoid algae liquid, stand-by,
(1.2) processed is carried out to algae:: configuration concentration be the fixing algae reagent of 5vol.% phenylacrolein solution and respectively configuration concentration be that the cosolvent acetone soln of 20vol.%, 40vol.%, 60vol.% and 80vol.% is stand-by, the chroococcoid algae liquid after the cultivation obtained by (1.1) step is drawn with glue head dropper, in injection centrifuge tube, centrifuge tube symmetry is put into whizzer, balance between two, carry out centrifugal with the rotating speed of 7000r/min, remove supernatant liquor in centrifuge tube after centrifugal 5min and repeat aforesaid operations until collect the chroococcoid sedimentation cell of 5mL, the concentration injecting above-mentioned configuration in the centrifuge tube leaving chroococcoid sedimentation cell is the phenylacrolein solution that 5vol.% fixes algae reagent, 3h is left standstill after mixing, supernatant liquor is removed by after the centrifugal 7min of chroococcoid sedimentation cell after fixing, then in centrifuge tube, inject deionized water and mix, supernatant liquor is removed after recentrifuge 7min, repeated washing 3 times, rotating speed used is 5000r/min, the concentration adding above-mentioned configuration in the centrifuge tube leaving the chroococcoid sedimentation cell after fixing is the cosolvent acetone soln of 20vol.% and mixes, centrifugal 3min after dehydration 20min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent acetone soln of 40vol.% and mixes, centrifugal 3min after dehydration 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent acetone soln of 60vol.% and mixes, centrifugal 3min after dehydration 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent acetone soln of 80vol.% and mixes, centrifugal 3min after dehydration 17min, above-mentioned dehydration and centrifugally operated twice is repeated again with anhydrous cosolvent acetone, obtain the chroococcoid that processed is crossed thus,
Second step, has the performance optimization process of the natural minerals of the emitting far-infrared function of energy:
The natural minerals mullite block with the emitting far-infrared function of energy is first tentatively broken into the small-particle of diameter at 2mm, stand-by, be mullite in mass ratio: ball milling ball: pour in ball grinder after cosolvent acetone=1:3:2 mixing, with the rotating speed ball milling 2h of 1200r/min, the product of this wet ball grinding is put into baking oven dry, temperature is set to 80 DEG C, and the time is 6h, calcined by mullite after drying, calcining temperature is 900 DEG C; Mullite after calcining is sieved, take out granularity be 300 ~ 100 objects heat treated have can the natural minerals mullite of emitting far-infrared function stand-by;
3rd step, the preparation of hollow glass micropearl:
(3.1) preparing base soln: 4mL tetraethoxy and 16mL cosolvent are hybridly prepared into solution A by the volume ratio of 1:4, is that the potassium hydroxide solution of 27%, 20mL deionized water and 15mL cosolvent are by volume for the ratio of 1:4:3 is hybridly prepared into B solution by 5mL mass percent concentration;
(3.2) hollow silica microsphere is prepared: get the 40mL B solution that (3.1) step prepares, adding volume is wherein the chroococcoid that the processed of 3mL is crossed, supersound process 4min, ensure that chroococcoid frustule forms suspension in solution B, make chroococcoid frustule surface planar water and alkali quickly and evenly, this suspension is put on magnetic stirring apparatus and stirs, the solution A that (3.1) step prepares is added drop-wise in the suspension on agitator, to ensure the SiO formed
2colloidal particle is evenly wrapped in chroococcoid frustule surface, form a kind of mixed solution, the mullite that 0.4g is heat treated is added in this mixed solution, at room temperature Keep agitation 48h, ageing 12h under room temperature, with the rotating speed collected by centrifugation product of 6000r/min, and with deionized water, centrifuge washing is carried out to product, products therefrom is dried, temperature is set to 60 DEG C, hollow microsphere is obtained again by retort furnace calcining, during calcining, temperature rise rate is 4 DEG C/min, calcining temperature is 600 DEG C, soaking time is 7h, obtained hollow silica microsphere and hollow glass micropearl thus.
Embodiment 4
Except the mixed algae of any amount of to be used instead by cytoalgae as cytoalgae and chlorella, formaldehyde is used instead outside the mixture into any amount of formaldehyde and acetaldehyde, and other are with embodiment 1.
Embodiment 5
Except the mixed algae of any amount of to be used instead by cytoalgae as cytoalgae, chlorella and chroococcoid, formaldehyde is used instead outside the mixture into any amount of formaldehyde and phenylacrolein, and other are with embodiment 1.
Embodiment 6
Except the mixed algae of any amount of to be used instead by chlorella as chlorella and chroococcoid, acetaldehyde is used instead outside the mixture into any amount of acetaldehyde and phenylacrolein, and other are with embodiment 2.
Embodiment 7
Except the mixed algae of any amount of to be used instead by chroococcoid as chroococcoid and cytoalgae, phenylacrolein is used instead outside the mixture into any amount of formaldehyde, acetaldehyde and phenylacrolein, and other are with embodiment 3.
Embodiment 8
Except being used instead by tourmalinite as except chromite, other are with embodiment 1.
Embodiment 9
Except being used instead by tourmalinite as except zircon sand, other are with embodiment 1.
Embodiment 10
Except the mixture used instead by trichroite as any amount of trichroite and zircon sand, other are with embodiment 2.
Embodiment 11
Except the mixture used instead by trichroite as any amount of trichroite and tourmalinite, other are with embodiment 2.
Embodiment 12
Except the mixture used instead by trichroite as any amount of trichroite and mullite, other are with embodiment 2.
Embodiment 13
Except the mixture used instead by trichroite as any amount of trichroite and mullite, other are with embodiment 2.
Embodiment 14
Except the mixture used instead by trichroite as any amount of trichroite and chromite, other are with embodiment 2.
Embodiment 15
Except the mixture used instead by trichroite as any amount of trichroite and zircon sand, other are with embodiment 2.
Embodiment 16
Except the mixture used instead by mullite as any amount of mullite and zircon sand, other are with embodiment 3.
Embodiment 17
Except the mixture used instead by mullite as any amount of mullite and tourmalinite, other are with embodiment 3.
Embodiment 18
Except the mixture used instead by mullite as any amount of mullite and chromite, other are with embodiment 3.
Embodiment 19
Except the mixture used instead by mullite as any amount of mullite, chromite and zircon sand, other are with embodiment 3.
Embodiment 20
Except the mixture used instead by mullite as any amount of mullite, trichroite and tourmalinite, other are with embodiment 3.
Embodiment 21
Except the mixture used instead by mullite as any amount of mullite, trichroite, tourmalinite and chromite, other are with embodiment 3.
Embodiment 22
Except the mixture used instead by mullite as any amount of mullite, trichroite, tourmalinite, chromite and zircon sand, other are with embodiment 3.
Embodiment 23
Except the mixture used instead by tourmalinite as any amount of tourmalinite, trichroite and zircon sand, other are with embodiment 1.
Embodiment 24
Except the mixture used instead by tourmalinite as any amount of tourmalinite, trichroite and chromite, other are with embodiment 1.
Embodiment 25
Except the mixture used instead by tourmalinite as any amount of tourmalinite, mullite, trichroite and zircon sand, other are with embodiment 1.
Embodiment 26
Except the mixture used instead by trichroite as any amount of trichroite, chromite and zircon sand, other are with embodiment 2.
Get hollow glass micropearl prepared by 3% any one embodiment above-mentioned as paint additive, obtained coating and basic components coating through same way brush same size, specification is in the foursquare glass test sample plate of 30.0cm × 30.0cm, carries out the test of effect of heat insulation.Test uses 150W infrared lamp analog light source, and is placed in about 15cm place directly over test sample plate, and test is positioned at the room temps up and down of the test sample plate of enclosed space, and investigate the space temperature difference, the test duration is 60min.By to the effect of heat insulation of two pieces of test sample plate in time-change of temperature observes and can find out, after test duration 10min, the temperature difference of the enclosed space up and down of the coating gained model obtained as paint additive with hollow glass micropearl prepared by this 3% any one embodiment above-mentioned tends to be steady; During test duration 20min, reach the stable temperature difference up to 39.7 DEG C, improve about 5.7 DEG C than the effect of heat insulation of basic components coating gained model.Visible, the hollow glass micropearl obtained by the inventive method has good effect of heat insulation.Simultaneously, it selects algae as raw material as biological template method, the natural minerals with the emitting far-infrared function of energy is adopted to optimize gained glass microballon structure, non-toxic by-products generates, a kind ofly prepare the novel method with special construction material, its have significantly be better than currently available technology large adopt prepare glass microballon method economy, the feature of environmental protection, security.
Starting material used in above-described embodiment are all by commercially available, and operating procedure is that those skilled in the art know.
Claims (6)
1. a preparation method for hollow glass micropearl, is characterized in that concrete steps are as follows:
The first step, the preparation of algae:
(1.1) algae is cultivated: the mother liquor preparing Algae culture solution by the formula of BG11 liquid nutrient medium, to this mother liquor, in the deionized water of experiment and algae seeded process, the glassware used carries out autoclave sterilization, after cooling according to the proportioning of BG11 nutrient solution, mother liquor is mixed with deionized water constant volume and is made into algae culturing liquid, algae kind being moved into is equipped with in the culturing bottle of algae culturing liquid, finally culturing bottle is put into growth cabinet to cultivate 15 ~ 20 days, culture temperature is 25 ~ 35 DEG C, intensity of illumination 1900 ~ 2100lx, light application time is 10 ~ 15h, pH value is 7.5 ~ 8.5, obtained cultivation algae algae liquid, stand-by,
(1.2) processed is carried out to algae: configuration concentration be the fixing algae reagent of 3vol.% ~ 5vol.% solution and respectively configuration concentration be the cosolvent solution for later use of 20vol.%, 40vol.%, 60vol.% and 80vol.%, draw by the obtained cultivation algae algae liquid of (1.1) step with glue head dropper, in injection centrifuge tube, centrifuge tube symmetry is put into whizzer, balance between two, carry out centrifugal with the rotating speed of 5000 ~ 7000r/min, supernatant liquor in centrifuge tube is removed after centrifugal 5 ~ 7min, repeat aforesaid operations until collect the algae sedimentation cell of 2 ~ 5mL, the concentration injecting above-mentioned configuration in the centrifuge tube leaving algae sedimentation cell is the solution that 3 ~ 5vol.% fixes algae reagent, 1 ~ 3h is left standstill after mixing, supernatant liquor is removed by after centrifugal for algae suspension liquid 5 ~ 7min, then in centrifuge tube, inject deionized water and mix, supernatant liquor is removed after recentrifuge 5 ~ 7min, repeated washing 3 times, rotating speed used is 5000 ~ 7000r/min, the concentration adding above-mentioned configuration in the centrifuge tube leaving the algae sedimentation cell after fixing is the cosolvent solution of 20vol.% and mixes, centrifugal 3 ~ 7min after dehydration 10 ~ 20min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 40vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 60vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, the concentration adding above-mentioned configuration after removing supernatant liquor is the cosolvent solution of 80vol.% and mixes, centrifugal 3 ~ 7min after dehydration 12 ~ 17min, above-mentioned dehydration and centrifugally operated twice is repeated again with anhydrous cosolvent, obtain the algae that processed is crossed thus,
Second step, has the performance optimization process of the natural minerals of the emitting far-infrared function of energy:
The natural minerals block with the emitting far-infrared function of energy is first tentatively broken into the small-particle of diameter at 1 ~ 2mm, stand-by, in mass ratio for having the natural minerals of the emitting far-infrared function of energy: ball milling ball: cosolvent=1:3:1.5 ~ 2 are poured in ball grinder after mixing, with the rotating speed ball milling 2 ~ 3h of 1000 ~ 1200r/min, the product of this wet ball grinding is put into baking oven dry, temperature is set to 60 ~ 80 DEG C, time is 6 ~ 8h, the natural minerals with the emitting far-infrared function of energy after drying is calcined, calcining temperature is 700 ~ 900 DEG C, having after calcining can the natural minerals of emitting far-infrared function be sieved, take out granularity be 300 ~ 100 objects heat treated have can the natural minerals of emitting far-infrared function stand-by,
3rd step, the preparation of hollow glass micropearl:
(3.1) preparing base soln: 2 ~ 4mL tetraethoxy and 8 ~ 16mL cosolvent are hybridly prepared into solution A by the volume ratio of 1:4, is that the alkaline solution of 27%, 4 ~ 20mL deionized water and 3 ~ 15mL cosolvent are by volume for the ratio of 1:4:3 is hybridly prepared into B solution by 1 ~ 5mL mass percent concentration;
(3.2) hollow silica microsphere is prepared: get 8 ~ 40mL B solution that (3.1) step prepares, adding volume is wherein the algae that processed that the first step of 3mL obtains is crossed, supersound process 2 ~ 4min, ensure that frustule forms suspension in solution B, make frustule surface planar water and alkali quickly and evenly, this suspension is put on magnetic stirring apparatus and stirs, the solution A that (3.1) step prepares dropwise is added drop-wise in the suspension on agitator, to ensure the SiO formed
2colloidal particle is evenly wrapped in frustule surface, form a kind of mixed solution, the natural minerals with the emitting far-infrared function of energy that 0.2 ~ 0.4g is heat treated is added in this mixed solution, at room temperature Keep agitation 24 ~ 48h, ageing 12 ~ 36h under room temperature, with the rotating speed collected by centrifugation product of 6000r/min, and with deionized water, centrifuge washing is carried out to product, products therefrom is dried, temperature is set to 40 ~ 60 DEG C, hollow microsphere is obtained again by retort furnace calcining, during calcining, temperature rise rate is 2 ~ 4 DEG C/min, calcining temperature is 500 ~ 600 DEG C, soaking time is 7 ~ 9h, obtained hollow silica microsphere and hollow glass micropearl thus.
2. the preparation method of a kind of hollow glass micropearl according to claim 1, is characterized in that: described algae is 1 ~ 3 kind in cytoalgae, chlorella or chroococcoid.
3. the preparation method of a kind of hollow glass micropearl according to claim 1, is characterized in that: described fixing algae reagent is 1 ~ 3 kind in formaldehyde, acetaldehyde or phenylacrolein.
4. the preparation method of a kind of hollow glass micropearl according to claim 1, is characterized in that: the emitting far-infrared function natural minerals of described energy is 1 ~ 5 kind in trichroite, mullite, tourmalinite, chromite or zircon sand.
5. the preparation method of a kind of hollow glass micropearl according to claim 1, is characterized in that: described alkali is strong aqua, sodium hydroxide or potassium hydroxide.
6. the preparation method of a kind of hollow glass micropearl according to claim 1, is characterized in that: described cosolvent is ethanol, propyl alcohol or acetone.
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