CN108993438A - A kind of preparation method of silicon substrate magnetic silica microballoon - Google Patents
A kind of preparation method of silicon substrate magnetic silica microballoon Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
Abstract
The invention discloses a kind of preparation methods of silicon substrate magnetic silica microballoon, belong to adsorbent material technical field.Casein is first dispersed in water by the present invention, adds urea, after adjusting pH, iron salt solutions is added dropwise, constant temperature is stirred to react obtained forerunner's dispersion liquid；After again mixing forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion, esters of silicon acis dilution is added dropwise, after reacted, silicon substrate presoma is made；By silicon substrate presoma under inert gas shielding state, slowly heating charing, is further warming up to 1500~1550 DEG C, cooling after 3~5h of pyroreaction, and discharging obtains carbonized material；By gained carbonized material and ring penta 2 are dilute mixed in mass ratio for 1:3~1:5 after, under nitrogen protection state, heating stirring reaction, then through cooling, filtering, washing and dry to get silicon substrate magnetic silica microballoon.The silicon substrate magnetic silica microballoon of technical solution of the present invention preparation has the characteristics that also have large specific surface area and porosity high while excellent absorption property.
Description
Technical field
The invention discloses a kind of preparation methods of silicon substrate magnetic silica microballoon, belong to adsorbent material technical field.
Background technique
Magnetic Nano material is a member in nano material big family, not only has the special nature of nano material, together
When also show superparamagnetism.And magnetic nano composite microsphere is then that magnetic Nano material is modified through organic or inorganic substance, changed
What property was prepared, be one kind have it is more multi-functional, using more extensive nano material, suffered from numerous areas very strong
Application potential, the utilization especially in terms of biomedical and chemical sensor are even more the hot spot of research.Magnetic silica is compound
The research of microballoon is even more to be a dark horse, in immobilised enzymes, targeted drug, DNA and RNA separation, magnetic-heat therapy, protein absorption point
From and chemical biosensor etc. suffer from very strong application potential.
The more prominent advantage of magnetic silicon dioxide composite microsphere mainly has: 1. good mechanical property, has compared with Large ratio surface
Product, bonding power are high；2. there is a large amount of silicone hydroxyl on surface, hydrophily is strong, is easy with method modification physically or chemically or modifies,
Higher bioactivity, and the larger promotion of biocompatibility are made it have, is a kind of good magnetic bio material；3. surface layer
Silica can more effectively get rid of the magnetic dipoles interaction between magnetic nano-particle；4. surface layer silica energy
Extraneous acid condition is prevented to corrode magnetic nanoparticle, and silica stability is high, can effectively improve the dispersion of microballoon
The swelling of stability and inhibition microballoon in organic solution, makes microballoon can apply to organic and inorganic solution；5. silica is compound
Microballoon also has the characteristics that porous, its catalytic activity and adsorptivity can be improved by the size and structure of control hole.
And traditional silicon substrate magnetic silica microballoon is when making and using, in order to improve absorption property and specific surface area,
When improving porosity, due to corrosive medium be easily accessible it is internal to corrode internal ferroso-ferric oxide, and by kernel
After package, porosity can reduce again, influence the contradiction of the absorption property of product.Therefore, how to improve traditional silicon substrate magnetism dioxy
The shortcomings that SiClx microballoon, is that it is promoted and is applied to broader field, meets industry to obtain the promotion of more high combination property
Production requirement urgent problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it is being made and used for traditional silicon substrate magnetic silica microballoon
When, in order to improve absorption property and specific surface area, when improving porosity, since corrosive medium is easily accessible inside to internally
Portion's ferroso-ferric oxide corrodes, and after kernel is wrapped up, porosity can reduce again, the contradiction of the absorption property of product is influenced,
Provide a kind of preparation method of silicon substrate magnetic silica microballoon.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of silicon substrate magnetic silica microballoon, specific preparation step are as follows:
(1) casein is dispersed in water for 1:20~1:30 in mass ratio, adds urea, adjust pH to 7.5~8.0, with
Iron salt solutions are slowly added dropwise under constant temperature stirring afterwards, after iron salt solutions are added dropwise, continue constant temperature be stirred to react 3~
5h obtains forerunner's dispersion liquid；
It (2) is in mass ratio after 1:1~3:1 is stirred, to be slowly added dropwise by forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion
The esters of silicon acis dilution of forerunner's dispersion liquid quality 30~50% continues to be stirred to react 3 after esters of silicon acis dilution is added dropwise
~5h, using filter, washing and drying obtain silicon substrate presoma；
(3) by silicon substrate presoma under inert gas shielding state, slowly heating charing, is further warming up to 1500~1550
DEG C, cooling after 3~5h of pyroreaction, discharging obtains carbonized material；
(4) by gained carbonized material and ring penta 2 it is dilute in mass ratio for 1:3~1:5 mix after, under nitrogen protection state, heating is stirred
Reaction is mixed, then through cooling, filtering, washing and drying are to get silicon substrate magnetic silica microballoon.
Step (1) is described to be slowly added dropwise to be added dropwise with 3~5mL/min rate.
Step (1) described iron salt solutions are the iron salt solutions that mass fraction is 8~10%；The molysite is ferric nitrate, chlorination
Any one in iron or ferric sulfate.
Step (2) the enzymatic hydrolysis chitosan dispersion preparation process are as follows: the chitosan and water for being 85~90% by deacetylation
After being dispersed with stirring in mass ratio for 1:10~1:15, the chitosan enzyme of chitosan mass 3~5% is added, constant temperature stirring digests,
Chitosan dispersion must be digested.
Step (2) is described to be slowly added dropwise to be added dropwise with 1~2mL/min rate.
Step (2) the esters of silicon acis dilution is by esters of silicon acis and dehydrated alcohol be in mass ratio 1:1~1:3 prepare and
At；The esters of silicon acis is any one in methyl orthosilicate, ethyl orthosilicate or positive silicic acid propyl ester.
Step (3) inert gas is any one in nitrogen, argon gas or helium.
Step (3) the slow heating charcoal, which is turned to, is warming up to 500~550 DEG C with 0.6~0.8 DEG C/min rate program, protects
1~2h of temperature charing.
The beneficial effects of the present invention are:
Technical solution of the present invention dissolves dispersion first using casein as absorption carrier, using urea auxiliary casein in water
Meanwhile using urea as precipitating reagent, urea slowly hydrolyzes iron ion combination in the hydroxide ion and iron salt solutions of generation and is formed
Iron hydroxide nucleus, and once have the generation of iron hydroxide nucleus that can be adsorbed by casein, effectively prevent iron hydroxide crystal
Reunion and further growth, so that its size is positively retained at nanoscale and be well dispersed in casein solution system, formed with
Casein is kernel, and iron hydroxide is the core-shell microspheres structure of shell, in subsequent processes, successively in iron hydroxide
Case surface cladding enzymatic hydrolysis chitosan and silica are to be made the silicon substrate presoma of multi-layer core-shell structure, from kernel to shell
It is followed successively by casein-iron hydroxide-enzymatic hydrolysis chitosan-silicon dioxide, in subsequent heating carbonization process, casein and enzymatic hydrolysis shell
Both organic matters of glycan, which occur to carbonize, simultaneously forms carbonaceous skeleton, and iron hydroxide dehydration is changed into iron oxide, and due to layer with
The thermal expansion coefficient of various composition and the difference of thermal coefficient between layer structure, cause multilayered structure that different degrees of receipts occur
Contracting, to form multilayered fold structure, the formation of pleated structure, which has, is conducive to make interiors of products to form multilayer absorption place, makes product
Specific surface area is effectively promoted, furthermore, with increasing into one for temperature, the good reproducibility of carbonaceous skeleton can will be contacted
Iron oxide portion be reduced to ferroso-ferric oxide and iron simple substance, and part carbonaceous skeleton under the high temperature conditions can also with contact
Silica between form the bonding of carbon-chemistry of silicones, so that the binding force between layer and layer structure be made to get a promotion, in addition,
In the subsequent and dilute reaction process of ring penta 2, fe can generate ferrocene structure with dilute react of ring penta 2, to aoxidize three four
Iron surface forms one layer of hydrophobic structure, and the presence of ferrocene not only can avoid acid, aqueous alkali invades internal ferroso-ferric oxide
Erosion also can avoid Oxidant and corrode it, hold to effectively solve the abundant rear internal magnetic core of traditional product porosity
The drawbacks of being easily corroded.
Specific embodiment
Casein and water are mixed for 1:20~1:30 in mass ratio and poured into No. 1 beaker, is stirred 20 with glass bar
After~30min, then into No. 1 beaker urea is added, adjusts material pH to 7.5~8.0 in No. 1 beaker, then No. 1 beaker is moved to
Digital display tests the speed constant temperature blender with magnetic force, in temperature be 45~50 DEG C, under the conditions of speed of agitator is 300~500r/min, side constant temperature
The iron salt solutions that mass fraction is 8~10% are slowly added dropwise with 3~5mL/min rate into No. 1 beaker for stirring side, molten to molysite
After liquid is added dropwise, continues constant temperature and be stirred to react 3~5h, obtain forerunner's dispersion liquid；The chitosan for being 85~90% by deacetylation
In mass ratio it is that 1:10~1:15 mixing is poured into No. 2 beakers with water, after being dispersed with stirring 10~20min with glass bar, adds
The chitosan enzyme of chitosan mass 3~5% is 35~40 DEG C in temperature, and under the conditions of revolving speed is 300~500r/min, constant temperature is stirred
30~45min is digested, enzymatic hydrolysis chitosan dispersion is obtained；In mass ratio it is 1 by forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion:
1~3:1 is poured into four-hole boiling flask, after being stirred 10~20min with blender with 300~400r/min revolving speed, in stirring shape
The silicic acid of forerunner's dispersion liquid quality 30~50% is added dropwise under state with 1~2mL/min rate into four-hole boiling flask by dropping funel
Ester dilution continues to be stirred to react 3~5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and use dehydrated alcohol
Washing filter residue 3~5 times, then by the filter residue vacuum freeze drying after washing, obtain silicon substrate presoma；Gained silicon substrate presoma is transferred to
In retort, and inert gas is passed through into furnace with 600~800mL/min rate, under inert gas shielding state, with 0.6
~0.8 DEG C/min rate program is warming up to 500~550 DEG C, after 1~2h of heat preservation charing, continue with 10~15 DEG C/min rate into
One step is warming up to 1500~1550 DEG C, after 3~5h of pyroreaction, cools to room temperature with the furnace, discharges, obtains carbonized material；By gained charcoal
Material and dilute mix in mass ratio for 1:3~1:5 of ring penta 2 are poured into reaction kettle, then nitrogen is passed through into reaction kettle, until setting
Swap out all air, then in temperature be 300~320 DEG C, revolving speed be 200~300r/min under the conditions of, heating stirring reaction 2~
4h is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, and after washing filter cake 3~5 times with dehydrated alcohol, then spends
Ion water washing 3~5 times, the filter cake after then washing deionized water is transferred in vacuum oven, in temperature be 95~105
DEG C, under the conditions of pressure is 60~80Pa, it is dried under vacuum to constant weight, discharges, obtains silicon substrate magnetic silica microballoon.The molysite is
Any one in ferric nitrate, iron chloride or ferric sulfate.The esters of silicon acis dilution is by esters of silicon acis and dehydrated alcohol by quality
Than being formulated for 1:1~1:3；The esters of silicon acis is any one in methyl orthosilicate, ethyl orthosilicate or positive silicic acid propyl ester
Kind.The inert gas is any one in nitrogen, argon gas or helium.
Casein and water are mixed for 1:30 in mass ratio and poured into No. 1 beaker, after being stirred 30min with glass bar,
Urea is added into No. 1 beaker again, adjusts material pH to 8.0 in No. 1 beaker, then No. 1 beaker is moved into digital display and is tested the speed constant temperature magnetic
Power blender, in temperature be 50 DEG C, speed of agitator be 500r/min under the conditions of, while constant temperature stirring while with 5mL/min rate to No. 1
The iron salt solutions that mass fraction is 10% are slowly added dropwise in beaker, after iron salt solutions are added dropwise, continue constant temperature and is stirred to react
5h obtains forerunner's dispersion liquid；By deacetylation be 90% chitosan and water be in mass ratio 1:15 mix pour into No. 2 beakers,
After being dispersed with stirring 20min with glass bar, add the chitosan enzyme of chitosan mass 5%, in temperature be 40 DEG C, revolving speed 500r/
Under the conditions of min, constant temperature stirring enzymatic hydrolysis 45min obtains enzymatic hydrolysis chitosan dispersion；By forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion
Liquid is that 3:1 is poured into four-hole boiling flask in mass ratio, after being stirred 20min with blender with 400r/min revolving speed, in stirring shape
The esters of silicon acis dilution of forerunner's dispersion liquid quality 50% is added dropwise under state with 2mL/min rate into four-hole boiling flask by dropping funel
Liquid continues to be stirred to react 5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and wash filter residue 5 with dehydrated alcohol
It is secondary, then by the filter residue vacuum freeze drying after washing, obtain silicon substrate presoma；Gained silicon substrate presoma is transferred in retort, and
Inert gas is passed through into furnace with 800mL/min rate, under inert gas shielding state, with 0.8 DEG C/min rate program liter
Temperature after heat preservation charing 2h, continues to further heat up with 15 DEG C/min rate to 1550 DEG C, after pyroreaction 5h, with furnace to 550 DEG C
It is cooled to room temperature, discharges, obtain carbonized material；Dilute mix in mass ratio for 1:5 of gained carbonized material and ring penta 2 is poured into reaction kettle,
Nitrogen is passed through into reaction kettle again, is then 320 DEG C in temperature, revolving speed is 300r/min condition until displacing all air
Under, heating stirring reacts 4h, is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, and wash filter cake with dehydrated alcohol
It after 5 times, then is washed with deionized 5 times, the filter cake after then washing deionized water is transferred in vacuum oven, is in temperature
105 DEG C, under the conditions of pressure is 80Pa, it is dried under vacuum to constant weight, discharges, obtains silicon substrate magnetic silica microballoon.The molysite is
Ferric nitrate.The esters of silicon acis dilution is formulated in mass ratio for 1:3 by esters of silicon acis and dehydrated alcohol；The esters of silicon acis is
Methyl orthosilicate.The inert gas is nitrogen.
Casein and water are mixed for 1:30 in mass ratio and poured into No. 1 beaker, after being stirred 30min with glass bar,
Sodium hydroxide solution is added into No. 1 beaker again, adjusts material pH to 8.0 in No. 1 beaker, then No. 1 beaker is moved into digital display and is surveyed
Fast constant temperature blender with magnetic force, in temperature be 50 DEG C, speed of agitator be 500r/min under the conditions of, while constant temperature stirring while with 5mL/min
The iron salt solutions that mass fraction is 10% are slowly added dropwise into No. 1 beaker for rate, after iron salt solutions are added dropwise, continue constant temperature
It is stirred to react 5h, obtains forerunner's dispersion liquid；By deacetylation be 90% chitosan and water be in mass ratio 1:15 mix pour into 2
In number beaker, after being dispersed with stirring 20min with glass bar, the chitosan enzyme of chitosan mass 5% is added, is 40 DEG C in temperature, turns
Under the conditions of speed is 500r/min, constant temperature stirring enzymatic hydrolysis 45min obtains enzymatic hydrolysis chitosan dispersion；By forerunner's dispersion liquid and enzymatic hydrolysis
Chitosan dispersion is that 3:1 is poured into four-hole boiling flask in mass ratio, is stirred 20min with blender with 400r/min revolving speed
Afterwards, forerunner's dispersion liquid quality 50% is added dropwise into four-hole boiling flask with 2mL/min rate by dropping funel under stirring
Esters of silicon acis dilution continues to be stirred to react 5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and use dehydrated alcohol
Washing filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtain silicon substrate presoma；Gained silicon substrate presoma is transferred to charcoal
Change in furnace, and inert gas is passed through into furnace with 800mL/min rate, under inert gas shielding state, with 0.8 DEG C/min speed
Rate temperature programming after heat preservation charing 2h, continues to further heat up with 15 DEG C/min rate to 1550 DEG C, pyroreaction to 550 DEG C
After 5h, room temperature is cooled to the furnace, discharge, obtain carbonized material；Dilute mix in mass ratio for 1:5 of gained carbonized material and ring penta 2 is poured into
In reaction kettle, then it is passed through nitrogen into reaction kettle, is then 320 DEG C in temperature, revolving speed is until displacing all air
Under the conditions of 300r/min, heating stirring reacts 4h, is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, and with anhydrous
It after ethanol washing filter cake 5 times, then is washed with deionized 5 times, the filter cake after then washing deionized water is transferred to vacuum drying
In case, it is 105 DEG C in temperature, under the conditions of pressure is 80Pa, is dried under vacuum to constant weight, discharges, it is micro- to obtain silicon substrate magnetic silica
Ball.The molysite is ferric nitrate.The esters of silicon acis dilution is by esters of silicon acis and dehydrated alcohol be in mass ratio 1:3 prepare and
At；The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.
Casein and water are mixed for 1:30 in mass ratio and poured into No. 1 beaker, after being stirred 30min with glass bar,
Urea is added into No. 1 beaker again, adjusts material pH to 8.0 in No. 1 beaker, then No. 1 beaker is moved into digital display and is tested the speed constant temperature magnetic
Power blender, in temperature be 50 DEG C, speed of agitator be 500r/min under the conditions of, while constant temperature stirring while with 5mL/min rate to No. 1
The iron salt solutions that mass fraction is 10% are slowly added dropwise in beaker, after iron salt solutions are added dropwise, continue constant temperature and is stirred to react
5h obtains forerunner's dispersion liquid；Forerunner's dispersion liquid is poured into four-hole boiling flask, is stirred with blender with 400r/min revolving speed
After 20min, forerunner's dispersion liquid quality is added dropwise into four-hole boiling flask with 2mL/min rate by dropping funel under stirring
50% esters of silicon acis dilution continues to be stirred to react 5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and use nothing
Water-ethanol washs filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtains silicon substrate presoma；By gained silicon substrate presoma
It is transferred in retort, and inert gas is passed through into furnace with 800mL/min rate, under inert gas shielding state, with 0.8
DEG C/min rate program is warming up to 550 DEG C, after heat preservation charing 2h, continuation is further heated up with 15 DEG C/min rate to 1550 DEG C,
After pyroreaction 5h, room temperature is cooled to the furnace, discharge, obtain carbonized material；By gained carbonized material and ring penta 2 it is dilute in mass ratio be 1:5
Mixing is poured into reaction kettle, then nitrogen is passed through into reaction kettle, until displacing all air, is then 320 DEG C in temperature, is turned
Under the conditions of speed is 300r/min, heating stirring reacts 4h, is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, be used in combination
It after dehydrated alcohol washs filter cake 5 times, then is washed with deionized 5 times, the filter cake after then washing deionized water is transferred to vacuum
In drying box, it is 105 DEG C in temperature, under the conditions of pressure is 80Pa, is dried under vacuum to constant weight, discharges, obtain silicon substrate magnetism titanium dioxide
Silicon microballoon.The molysite is ferric nitrate.It is that 1:3 is prepared that the esters of silicon acis dilution is by esters of silicon acis and dehydrated alcohol in mass ratio
It forms；The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.
Casein and water are mixed for 1:30 in mass ratio and poured into No. 1 beaker, after being stirred 30min with glass bar,
Urea is added into No. 1 beaker again, adjusts material pH to 8.0 in No. 1 beaker, then No. 1 beaker is moved into digital display and is tested the speed constant temperature magnetic
Power blender, in temperature be 50 DEG C, speed of agitator be 500r/min under the conditions of, while constant temperature stirring while with 5mL/min rate to No. 1
The iron salt solutions that mass fraction is 10% are slowly added dropwise in beaker, after iron salt solutions are added dropwise, continue constant temperature and is stirred to react
5h obtains forerunner's dispersion liquid；By deacetylation be 90% chitosan and water be in mass ratio 1:15 mix pour into No. 2 beakers,
After being dispersed with stirring 20min with glass bar, add the chitosan enzyme of chitosan mass 5%, in temperature be 40 DEG C, revolving speed 500r/
Under the conditions of min, constant temperature stirring enzymatic hydrolysis 45min obtains enzymatic hydrolysis chitosan dispersion；By forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion
Liquid is that 3:1 is poured into four-hole boiling flask in mass ratio, after being stirred 20min with blender with 400r/min revolving speed, in stirring shape
The esters of silicon acis dilution of forerunner's dispersion liquid quality 50% is added dropwise under state with 2mL/min rate into four-hole boiling flask by dropping funel
Liquid continues to be stirred to react 5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and wash filter residue 5 with dehydrated alcohol
It is secondary, then by the filter residue vacuum freeze drying after washing, obtain silicon substrate presoma；Gained silicon substrate presoma and ring penta 2 is dilute by quality
It is poured into reaction kettle than being mixed for 1:5, then is passed through nitrogen into reaction kettle, until displacing all air, be then in temperature
320 DEG C, under the conditions of revolving speed is 300r/min, heating stirring reacts 4h, is cooled to room temperature, material filtering in reaction kettle obtains
Filter cake, and after washing filter cake 5 times with dehydrated alcohol, then be washed with deionized 5 times, the filter cake after then washing deionized water
It is transferred in vacuum oven, is 105 DEG C in temperature, under the conditions of pressure is 80Pa, is dried under vacuum to constant weight, discharges, obtain silicon substrate magnetic
Property silicon dioxide microsphere.The molysite is ferric nitrate.The esters of silicon acis dilution be by esters of silicon acis and dehydrated alcohol in mass ratio
It is formulated for 1:3；The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.
Casein and water are mixed for 1:30 in mass ratio and poured into No. 1 beaker, after being stirred 30min with glass bar,
Urea is added into No. 1 beaker again, adjusts material pH to 8.0 in No. 1 beaker, then No. 1 beaker is moved into digital display and is tested the speed constant temperature magnetic
Power blender, in temperature be 50 DEG C, speed of agitator be 500r/min under the conditions of, while constant temperature stirring while with 5mL/min rate to No. 1
The iron salt solutions that mass fraction is 10% are slowly added dropwise in beaker, after iron salt solutions are added dropwise, continue constant temperature and is stirred to react
5h obtains forerunner's dispersion liquid；By deacetylation be 90% chitosan and water be in mass ratio 1:15 mix pour into No. 2 beakers,
After being dispersed with stirring 20min with glass bar, add the chitosan enzyme of chitosan mass 5%, in temperature be 40 DEG C, revolving speed 500r/
Under the conditions of min, constant temperature stirring enzymatic hydrolysis 45min obtains enzymatic hydrolysis chitosan dispersion；By forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion
Liquid is that 3:1 is poured into four-hole boiling flask in mass ratio, after being stirred 20min with blender with 400r/min revolving speed, in stirring shape
The esters of silicon acis dilution of forerunner's dispersion liquid quality 50% is added dropwise under state with 2mL/min rate into four-hole boiling flask by dropping funel
Liquid continues to be stirred to react 5h after esters of silicon acis dilution is added dropwise, and filtering obtains filter residue, and wash filter residue 5 with dehydrated alcohol
It is secondary, then by the filter residue vacuum freeze drying after washing, obtain silicon substrate presoma；Gained silicon substrate presoma is transferred in retort, and
Inert gas is passed through into furnace with 800mL/min rate, under inert gas shielding state, with 0.8 DEG C/min rate program liter
Temperature after heat preservation charing 2h, continues to further heat up with 15 DEG C/min rate to 1550 DEG C, after pyroreaction 5h, with furnace to 550 DEG C
It is cooled to room temperature, discharges, obtain carbonized material；Obtain silicon substrate magnetic silica microballoon.The molysite is ferric nitrate.The esters of silicon acis is dilute
Releasing liquid is formulated in mass ratio for 1:3 by esters of silicon acis and dehydrated alcohol；The esters of silicon acis is methyl orthosilicate.The inertia
Gas is nitrogen.
Comparative example: the silicon substrate magnetic silica microballoon of Wuxi new material Co., Ltd production.
Example 1 to the resulting silicon substrate magnetic silica microballoon of example 5 and comparative example product are subjected to performance detection, specifically
Detection method is as follows:
Porosity is measured using mercury injection apparatus (Autopore9500)；And survey its specific surface area.Ground conical flask is taken to number, it is accurate to claim
0.1g test specimen is taken, iron hydroxide is injected into conical flask, ground conical flask is sealed with preservative film, is placed in constant temperature oscillator
In, 25 DEG C of water temperature, oscillation rate 200rp/min, time of contact 12h are controlled, separates absorption using the syringe with filtering needle
Matter and test specimen measure adsorption efficiency.
Specific testing result is as shown in table 1:
The 1 specific testing result of silicon substrate magnetic silica microballoon of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Specific surface area/m2g-1 | 1983 | 1762 | 1627 | 1341 | 1212 | 1032 |
| Porosity/% | 94 | 87 | 84 | 81 | 78 | 62 |
| Adsorption efficiency/% | 57.3 | 35.7 | 36.8 | 30.1 | 34.2 | 21.1 |
By 1 testing result of table it is found that the silicon substrate magnetic silica microballoon of technical solution of the present invention preparation has excellent absorption
Also have the characteristics that large specific surface area and porosity are high while performance, has in the development of adsorbent material technology industry wide
Prospect.
Claims (8)
1. a kind of preparation method of silicon substrate magnetic silica microballoon, it is characterised in that specific preparation step are as follows:
(1) casein is dispersed in water for 1:20~1:30 in mass ratio, adds urea, adjust pH to 7.5~8.0, with
Iron salt solutions are slowly added dropwise under constant temperature stirring afterwards, after iron salt solutions are added dropwise, continue constant temperature be stirred to react 3~
5h obtains forerunner's dispersion liquid；
It (2) is in mass ratio after 1:1~3:1 is stirred, to be slowly added dropwise by forerunner's dispersion liquid and enzymatic hydrolysis chitosan dispersion
The esters of silicon acis dilution of forerunner's dispersion liquid quality 30~50% continues to be stirred to react 3 after esters of silicon acis dilution is added dropwise
~5h, using filter, washing and drying obtain silicon substrate presoma；
(3) by silicon substrate presoma under inert gas shielding state, slowly heating charing, is further warming up to 1500~1550
DEG C, cooling after 3~5h of pyroreaction, discharging obtains carbonized material；
(4) by gained carbonized material and ring penta 2 it is dilute in mass ratio for 1:3~1:5 mix after, under nitrogen protection state, heating is stirred
Reaction is mixed, then through cooling, filtering, washing and drying are to get silicon substrate magnetic silica microballoon.
2. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (1)
It is described to be slowly added dropwise to be added dropwise with 3~5mL/min rate.
3. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (1)
The iron salt solutions are the iron salt solutions that mass fraction is 8~10%；The molysite is in ferric nitrate, iron chloride or ferric sulfate
Any one.
4. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (2)
The enzymatic hydrolysis chitosan dispersion preparation process are as follows: by deacetylation be 85~90% chitosan and water be in mass ratio 1:10
After~1:15 is dispersed with stirring, the chitosan enzyme of chitosan mass 3~5% is added, constant temperature stirring enzymatic hydrolysis must digest chitosan point
Dispersion liquid.
5. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (2)
It is described to be slowly added dropwise to be added dropwise with 1~2mL/min rate.
6. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (2)
It is that 1:1~1:3 is formulated that the esters of silicon acis dilution is by esters of silicon acis and dehydrated alcohol in mass ratio；The esters of silicon acis is positive
Any one in methyl silicate, ethyl orthosilicate or positive silicic acid propyl ester.
7. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (3)
The inert gas is any one in nitrogen, argon gas or helium.
8. a kind of preparation method of silicon substrate magnetic silica microballoon according to claim 1, it is characterised in that step (3)
The slow heating charcoal, which is turned to, is warming up to 500~550 DEG C with 0.6~0.8 DEG C/min rate program, 1~2h of heat preservation charing.
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