CN109092240A - A kind of preparation method of porous magnetic hydroxylapatite microballoon - Google Patents
A kind of preparation method of porous magnetic hydroxylapatite microballoon Download PDFInfo
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- CN109092240A CN109092240A CN201811078382.4A CN201811078382A CN109092240A CN 109092240 A CN109092240 A CN 109092240A CN 201811078382 A CN201811078382 A CN 201811078382A CN 109092240 A CN109092240 A CN 109092240A
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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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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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
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
Abstract
The invention discloses a kind of preparation methods of porous magnetic hydroxylapatite microballoon, belong to porous adsorbing material preparation technical field.The present invention first preheats gelatin dispersion liquid, and emulsifier is dissolved in white oil, then the gelatin dispersion liquid after preheating is slowly added dropwise into the white oil for having dissolved emulsifier, and the gelatin dispersion liquid after preheating is added dropwise, cooling and stirring, filters, dry, obtains gelatine microsphere；It again disperses gelatine microsphere in iron salt solutions, adds precipitating reagent and adjust pH, and dopamine is added, low temperature is stirred to react, and primary cladding gelatine microsphere is made；Primary cladding gelatine microsphere is dispersed in water again, nanometer hydroxyapatite is added, esters of silicon acis then is added dropwise under constant temperature stirring, after being added dropwise, continues constant temperature and is stirred to react, filter, wash and dry, obtain secondary cladding microballoon；Then by after the charing of secondary cladding microballoon, pyroreaction, fumigated with humid carbon dioxide to get porous magnetic hydroxylapatite microballoon.
Description
Technical field
The invention discloses a kind of preparation methods of porous magnetic hydroxylapatite microballoon, belong to porous adsorbing material preparation
Technical field.
Background technique
In industrial processes, waste water, exhaust gas and solid waste (i.e. " three industrial wastes ") can be generally generated, is arranged in violation of rules and regulations
Putting " three industrial wastes " can cause environmental pollution.An important component in " three industrial wastes " is industrial wastewater, it is
Refer to waste water, sewage and the waste liquid generated in industrial processes, therefore industrial wastewater typically contains the industrial production outflowed with water
Raw material, intermediate product and product.Compared with city domestic sewage, industrial wastewater water quality is more complicated, and pollutant load is higher, place
It is bigger to manage difficulty, this also gives traditional wastewater treatment method and technology to bring huge challenge, therefore researches and develops a system
The new method and new technology of column processing difference industrial wastewater are extremely urgent.Photocatalitic Technique of Semiconductor is the one of rising in recent years
The new technology of kind of processing waste water, organic pollutant that can thoroughly in degrading waste water using the technology, and secondary dirt is not generated
Dye.Meanwhile light is only consumed during using the technical treatment waste water, therefore it also has consersion unit simply and reaction item
The mild advantage of part.Compared with conventional physical facture and method of chemical treatment, Photocatalitic Technique of Semiconductor has certain advantage,
It has broad application prospects in field of industrial waste water treatment.Hydroxyapatite is a kind of more typical phosphate, at present in ridge
It is found in the mineral of the bone of Vertebrate, tooth and nature.With unique crystal structure and surface-active, therefore
With stronger adsorption capacity, it can pass through the huge sum of money in the fixed water body of ionic adsorption, ion exchange and dissolution-deposition
Belong to ion, moreover it is possible to the organic pollutant in removal water body be acted on by adsorption, therefore itself is a kind of function admirable
Material for water treatment.In addition, a kind of still more typical catalyst carrier material, can make in its area load different activities ingredient
The standby outstanding catalyst for more being applied to different field.
For traditional magnetic hydroxyapatite during the preparation process using ferroso-ferric oxide as kernel, hydroxyapatite is outer
Shell, binding force is insufficient between nucleocapsid, be easy to cause product in storage and use process between nucleocapsid it is peeling-off, lead to product
The substance of absorption carriage is lost, thus the drawbacks of influencing the adsorption effect and using effect of product.Therefore, how to improve tradition more
The shortcomings that hole magnetic hydroxylapatite microballoon, to obtain the promotion of more high combination property, be its promote with applied to broader
Field meets industrial production demand urgent problem to be solved.
Summary of the invention
The present invention solves the technical problem of: for traditional magnetic hydroxyapatite during the preparation process with four oxidations
Three-iron is kernel, and hydroxyapatite is shell, and binding force is insufficient between nucleocapsid, is easy to cause product in storage and use process
It is peeling-off between nucleocapsid, cause the substance of product absorption carriage to be lost, to influence the adsorption effect and using effect of product
The drawbacks of, provide a kind of preparation method of porous magnetic hydroxylapatite microballoon.In order to solve the above-mentioned technical problem, of the invention
Used technical solution is:
A kind of preparation method of porous magnetic hydroxylapatite microballoon, specific preparation step are as follows:
(1) according to parts by weight, 30~50 parts of gelatin dispersion liquids, 8~10 parts of emulsifiers are successively taken, 40~60 parts of white oils first will
The preheating of gelatin dispersion liquid, and emulsifier is dissolved in white oil, then the gelatin dispersion liquid after preheating is slowly added dropwise to dissolution
In the white oil of emulsifier, the gelatin dispersion liquid after preheating is added dropwise, cooling and stirring, is filtered, dry, obtains gelatine microsphere；
(2) it in mass ratio disperses gelatine microsphere in iron salt solutions for 1:5~1:10, under the conditions of temperature is 4~6 DEG C, then
Precipitating reagent is added, adjusts iron salt solutions pH to 8.0~8.5, and the dopamine of iron salt solutions quality 1~2% is added, continues low temperature
After being stirred to react 2~4h, filtering washs and dry, obtains and once coat gelatine microsphere；
(3) according to parts by weight, 60~80 parts of primary cladding gelatine microspheres are successively taken, 20~30 parts of esters of silicon acis, 10~20 parts are received
Primary cladding gelatine microsphere is first dispersed in water, adds nano-hydroxy-apatite by rice hydroxyapatite, 100~200 parts of water
Then esters of silicon acis is added dropwise under constant temperature stirring in stone, after being added dropwise, continues constant temperature and is stirred to react, filter, washs and dry
It is dry, obtain secondary cladding microballoon；
(4) by the secondary cladding microballoon of gained under inert gas shielding state, heating charing, then further heat up to 1500~
1550 DEG C, insulation reaction obtains carbonized material；
(5) by carbonized material under the conditions of 800~850 DEG C, after persistently fumigating 4~6h in humid carbon dioxide atmosphere, out
Material, alkali leaching, washing are dry to get porous magnetic hydroxylapatite microballoon.
It is that 1:8~1:10 is formulated that step (1) the gelatin dispersion liquid is by gelatin and water in mass ratio.
Step (1) emulsifier is emulsifier op-10, any one in Tween-60 or Si Pan -80.
Step (1) white oil is any one in 40# white oil, 45# white oil or 50# white oil.
Step (2) molysite is any one in ferric nitrate, iron chloride or ferric sulfate.
Step (2) precipitating reagent is any one in ammonium hydroxide or urea.
Step (3) esters of silicon acis is any one in methyl orthosilicate, ethyl orthosilicate or positive silicic acid propyl ester.
Step (4) inert gas is any one in nitrogen, helium or argon gas.
Step (5) the humid carbon dioxide gas is the carbon dioxide gas that moisture content is 3~5%.
The beneficial effects of the present invention are:
(1) technical solution of the present invention utilizes hydroxyl, carboxyl in gelatin molecule structure etc. first to make gelatine microsphere by oneself as kernel
The good adsorption properties that group provides, the iron hydroxide that adsorption precipitation generates, and once having iron hydroxide nucleus to be formed can be by
Gelatine microsphere adsorption effectively avoids the further growth and reunion of iron hydroxide nucleus, its size is made to be maintained at nanoscale,
To form one layer of uniform nanometer iron hydroxide clad on gelatine microsphere surface, then cooperate dopamine in weakly alkaline environment
Under, oxidation autohemagglutination can occur in nanometer iron hydroxide cover surface has to improve the absorption property of iron hydroxide clad
Conducive in 3 treatment process of subsequent step, the hydrolysate of esters of silicon acis is adsorbed, to fix again in iron hydroxide cover surface
The complex of one layer of nano silica and nanometer hydroxyapatite, under step 4 inert gas shielding state in carbonization process,
The organic matters such as dopamine and interior nucleogelatin carbonize, and form carbonaceous skeleton middle layer and kernel, and further with temperature
It increases, the carbonaceous ingredient in carbonaceous skeleton middle layer and kernel can form firm carbon-silicon between the silicon dioxide layer on surface
Chemical bonding, thus so that hydroxyapatite shell is securely anchored in core surface, and carbonaceous skeleton has good reducing property,
Iron hydroxide can be dehydrated to the iron oxide to be formed and be reduced to ferroso-ferric oxide kernel under the high temperature conditions, product is effectively prevented and exist
Separation in storage and use process between nucleocapsid, enables product absorption property and the permanently effective holding of load performance；
(2) technical solution of the present invention is by occurring the hydroxyapatite decomposed under hot conditions in humid carbon dioxide atmosphere
Regeneration, so that the biocompatibility of product be enable to be effectively retained, during subsequent alkaline leaching, residual silica can be dissolved
It is removed, to ensure the good porosity of product surface, product specific surface area is enable to be promoted, and inhaled in subsequent load
During attached, effective component is easier to penetrate into interiors of products, improves the adsorbance of product.
Specific embodiment
In mass ratio be 1:8~1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, stirred with glass bar
Mix 10~20min after, under room temperature stand swelling 6~8h, then in temperature be 60~65 DEG C, revolving speed be 300~
Under the conditions of 500r/min, constant temperature 30~40min of stirring and dissolving is cooling, obtains gelatin dispersion liquid, stand for standby use；According to parts by weight,
Successively take 30~50 parts of gelatin dispersion liquids, 8~10 parts of emulsifiers, 40~60 parts of white oils, gelatin dispersion liquid is first preheated to 58~
60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil, then the gelatin dispersion liquid after preheating is passed through into dropping funel
It being slowly added dropwise with 3~5mL/min rate into the white oil for having dissolved emulsifier, the gelatin dispersion liquid after preheating is added dropwise,
Three-necked flask is moved into ice-water bath, with blender with 300~500r/min revolving speed 30~45min of cooling and stirring, using filter,
No. 1 filter cake filter cake is obtained, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；It in mass ratio will be bright for 1:5~1:10
Glue microballoon is scattered in the iron salt solutions that mass fraction is 8~10%, is 4~6 DEG C in temperature, speed of agitator is 300~500r/
Under the conditions of min, precipitating reagent is added, adjusts iron salt solutions pH to 8.0~8.5, and the DOPA of iron salt solutions quality 1~2% is added
Amine, after continuation low temperature is stirred to react 2~4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 3~5 times, then will
No. 2 filter cakes after washing are transferred to drying in vacuum freezing drying oven, obtain and once coat gelatine microsphere；According to parts by weight, successively
Take 60~80 parts of primary cladding gelatine microspheres, 20~30 parts of esters of silicon acis, 10~20 parts of nanometer hydroxyapatites, 100~200 parts
Water first will once coat gelatine microsphere and water and be added in reaction kettle, and add nanometer hydroxyapatite, then in temperature be 45~
50 DEG C, under the conditions of revolving speed is 600~800r/min, esters of silicon acis is added dropwise into reaction kettle in constant temperature stirring, is added dropwise to esters of silicon acis
After, continue constant temperature and be stirred to react 2~3h, filter, obtain No. 3 filter cakes, and No. 3 filter cakes 2~3 of gained will be washed with deionized
It is secondary, then by No. 3 filter cake vacuum freeze dryings after washing, obtain secondary cladding microballoon；The secondary cladding microballoon of gained is transferred to charing
In furnace, inert gas is passed through into furnace with 400~500mL/min rate, under inert gas shielding state, with 4~6 DEG C/min
Rate program is warming up to 600~650 DEG C, after heat preservation carbonizes 2~4h, continues to be warming up to 1500 with 8~10 DEG C/min rate program
~1550 DEG C, 3~5h of insulation reaction, carbonized material is obtained, then cool to carbonized material with the furnace 800 under inert gas shielding state
~850 DEG C, stopping is passed through inert gas, and humid carbon dioxide gas is passed through into furnace with 200~300mL/min rate, in
After persistently fumigating 4~6h in humid carbon dioxide atmosphere, room temperature is cooled to the furnace, discharge, obtain green body, then by gained green body
It is impregnated in the sodium hydroxide solution that mass fraction is 8~10%, after 30~45min of ultrasonic immersing, filtering is washed and dry, i.e.,
Obtain porous magnetic hydroxylapatite microballoon.The emulsifier is emulsifier op-10, any one in Tween-60 or Si Pan -80
Kind.The white oil is any one in 40# white oil, 45# white oil or 50# white oil.The molysite is ferric nitrate, iron chloride or sulphur
Any one in sour iron.The precipitating reagent is any one in ammonium hydroxide or urea.The esters of silicon acis is methyl orthosilicate, just
Any one in silester or positive silicic acid propyl ester.The inert gas is any one in nitrogen, helium or argon gas.Institute
Stating humid carbon dioxide gas is the carbon dioxide gas that moisture content is 3~5%.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, and the DOPA of iron salt solutions quality 2% is added
Amine, after continuation low temperature is stirred to react 4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 5 times, then will be after washing
No. 2 filter cakes be transferred in vacuum freezing drying oven dry, obtain and once coat gelatine microsphere；According to parts by weight, 80 parts are successively taken
Primary cladding gelatine microsphere, 30 parts of esters of silicon acis, 20 parts of nanometer hydroxyapatites, 200 parts of water, first will once coat gelatine microsphere and
Water be added reaction kettle in, add nanometer hydroxyapatite, then in temperature be 50 DEG C, revolving speed be 800r/min under the conditions of, side
Esters of silicon acis is added dropwise into reaction kettle for constant temperature stirring side, after esters of silicon acis is added dropwise, continues constant temperature and is stirred to react 3h, filter, obtain 3
Number filter cake, and will be washed with deionized gained 3 filter cake 3 times, then by No. 3 filter cake vacuum freeze dryings after washing, obtain two
Secondary cladding microballoon；The secondary cladding microballoon of gained is transferred in retort, inert gas is passed through into furnace with 500mL/min rate,
Under inert gas shielding state, 650 DEG C, after heat preservation carbonizes 4h are warming up to 6 DEG C/min rate program, is continued with 10 DEG C/min
Rate program is warming up to 1550 DEG C, insulation reaction 5h, carbonized material is obtained, then by carbonized material under inert gas shielding state, with furnace
850 DEG C are cooled to, stopping is passed through inert gas, and humid carbon dioxide gas, Yu Chao are passed through into furnace with 300mL/min rate
After persistently fumigating 6h in wet carbon dioxide gas atmosphere, room temperature is cooled to the furnace, discharge, obtain green body, then gained green body is impregnated
In the sodium hydroxide solution that mass fraction is 10%, after ultrasonic immersing 45min, filtering, washing and drying are to get porous magnetic
Hydroxyapatite micro-sphere.The emulsifier is emulsifier op-10.The white oil is 40# white oil.The molysite is ferric nitrate.Institute
Stating precipitating reagent is ammonium hydroxide.The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.The humid carbon dioxide gas
The carbon dioxide gas for being 5% for moisture content.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, and the DOPA of iron salt solutions quality 2% is added
Amine, after continuation low temperature is stirred to react 4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 5 times, then will be after washing
No. 2 filter cakes be transferred in vacuum freezing drying oven dry, obtain and once coat gelatine microsphere；According to parts by weight, 80 parts are successively taken
Primary cladding gelatine microsphere, 30 parts of esters of silicon acis, 20 parts of nanometer hydroxyapatites, 200 parts of water, first will once coat gelatine microsphere and
Water be added reaction kettle in, add nanometer hydroxyapatite, then in temperature be 50 DEG C, revolving speed be 800r/min under the conditions of, side
Esters of silicon acis is added dropwise into reaction kettle for constant temperature stirring side, after esters of silicon acis is added dropwise, continues constant temperature and is stirred to react 3h, filter, obtain 3
Number filter cake, and will be washed with deionized gained 3 filter cake 3 times, then by No. 3 filter cake vacuum freeze dryings after washing, obtain two
Secondary cladding microballoon；The secondary cladding microballoon of gained is transferred in retort, inert gas is passed through into furnace with 500mL/min rate,
Under inert gas shielding state, 650 DEG C, after heat preservation carbonizes 4h are warming up to 6 DEG C/min rate program, obtains carbonized material, then will
Carbonized material cools to 850 DEG C with the furnace, stopping is passed through inert gas, and with 300mL/min rate under inert gas shielding state
It is passed through humid carbon dioxide gas into furnace, after persistently fumigating 6h in humid carbon dioxide atmosphere, cools to room with the furnace
Temperature, discharging obtain green body, then gained green body are impregnated in the sodium hydroxide solution that mass fraction is 10%, ultrasonic immersing 45min
Afterwards, it filters, washing and drying are to get porous magnetic hydroxylapatite microballoon.The emulsifier is emulsifier op-10.It is described white
Oil is 40# white oil.The molysite is ferric nitrate.The precipitating reagent is ammonium hydroxide.The esters of silicon acis is methyl orthosilicate.The inertia
Gas is nitrogen.The humid carbon dioxide gas is the carbon dioxide gas that moisture content is 5%.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, and the DOPA of iron salt solutions quality 2% is added
Amine, after continuation low temperature is stirred to react 4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 5 times, then will be after washing
No. 2 filter cakes be transferred in vacuum freezing drying oven dry, obtain and once coat gelatine microsphere；According to parts by weight, 80 parts are successively taken
Primary cladding gelatine microsphere, 30 parts of esters of silicon acis, 20 parts of nanometer hydroxyapatites, 200 parts of water, first will once coat gelatine microsphere and
Water be added reaction kettle in, add nanometer hydroxyapatite, then in temperature be 50 DEG C, revolving speed be 800r/min under the conditions of, side
Esters of silicon acis is added dropwise into reaction kettle for constant temperature stirring side, after esters of silicon acis is added dropwise, continues constant temperature and is stirred to react 3h, filter, obtain 3
Number filter cake, and will be washed with deionized gained 3 filter cake 3 times, then by No. 3 filter cake vacuum freeze dryings after washing, obtain two
Secondary cladding microballoon；The secondary cladding microballoon of gained is transferred in retort, inert gas is passed through into furnace with 500mL/min rate,
Under inert gas shielding state, 650 DEG C, after heat preservation carbonizes 4h are warming up to 6 DEG C/min rate program, is continued with 10 DEG C/min
Rate program is warming up to 1550 DEG C, insulation reaction 5h, carbonized material is obtained, then by carbonized material under inert gas shielding state, with furnace
850 DEG C are cooled to, stopping is passed through inert gas, and humidified nitrogen gas is passed through into furnace with 300mL/min rate, in moist nitrogen
After persistently fumigating 6h in gas atmosphere, room temperature is cooled to the furnace, discharged, obtain green body, then gained green body is impregnated in quality point
Number is in 10% sodium hydroxide solution, after ultrasonic immersing 45min, filtering, washing and drying is to get porous magnetic hydroxy-apatite
Stone microballoon.The emulsifier is emulsifier op-10.The white oil is 40# white oil.The molysite is ferric nitrate.The precipitating reagent
For ammonium hydroxide.The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, and the DOPA of iron salt solutions quality 2% is added
Amine, after continuation low temperature is stirred to react 4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 5 times, then will be after washing
No. 2 filter cakes be transferred in vacuum freezing drying oven dry, obtain and once coat gelatine microsphere；According to parts by weight, 80 parts are successively taken
Primary cladding gelatine microsphere, 30 parts of esters of silicon acis, 20 parts of nanometer hydroxyapatites, 200 parts of water, first will once coat gelatine microsphere and
Water be added reaction kettle in, add nanometer hydroxyapatite, then in temperature be 50 DEG C, revolving speed be 800r/min under the conditions of, side
Esters of silicon acis is added dropwise into reaction kettle for constant temperature stirring side, after esters of silicon acis is added dropwise, continues constant temperature and is stirred to react 3h, filter, obtain 3
Number filter cake, and will be washed with deionized gained 3 filter cake 3 times, then by No. 3 filter cake vacuum freeze dryings after washing, obtain two
Secondary cladding microballoon；The secondary cladding microballoon of gained is transferred in retort, inert gas is passed through into furnace with 500mL/min rate,
Under inert gas shielding state, 650 DEG C, after heat preservation carbonizes 4h are warming up to 6 DEG C/min rate program, is continued with 10 DEG C/min
Rate program is warming up to 1550 DEG C, insulation reaction 5h, carbonized material is obtained, then by carbonized material under inert gas shielding state, with furnace
850 DEG C are cooled to, stopping is passed through inert gas, and dry carbon dioxide gas, Yu Gan are passed through into furnace with 300mL/min rate
After persistently fumigating 6h in dry carbon dioxide gas atmosphere, room temperature is cooled to the furnace, discharge, obtain green body, then gained green body is impregnated
In the sodium hydroxide solution that mass fraction is 10%, after ultrasonic immersing 45min, filtering, washing and drying are to get porous magnetic
Hydroxyapatite micro-sphere.The emulsifier is emulsifier op-10.The white oil is 40# white oil.The molysite is ferric nitrate.Institute
Stating precipitating reagent is ammonium hydroxide.The esters of silicon acis is methyl orthosilicate.The inert gas is nitrogen.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, and the DOPA of iron salt solutions quality 2% is added
Amine, after continuation low temperature is stirred to react 4h, filtering obtains No. 2 filter cakes, and No. 2 filter cakes are washed with deionized 5 times, then will be after washing
No. 2 filter cakes be transferred in vacuum freezing drying oven dry, obtain and once coat gelatine microsphere；According to parts by weight, 80 parts are successively taken
It is micro- first will once to coat gelatin for primary cladding gelatine microsphere, 30 parts of butyl titanates, 20 parts of nanometer hydroxyapatites, 200 parts of water
Ball and water are added in reaction kettle, add nanometer hydroxyapatite, are then 50 DEG C in temperature, revolving speed is 800r/min condition
Under, butyl titanate is added dropwise into reaction kettle in constant temperature stirring, after butyl titanate is added dropwise, it is anti-to continue constant temperature stirring
3h is answered, filters, obtains No. 3 filter cakes, and will be washed with deionized gained 3 filter cake 3 times, then by No. 3 filter cake vacuum after washing
Freeze-drying, obtains secondary cladding microballoon；The secondary cladding microballoon of gained is transferred in retort, with 500mL/min rate into furnace
It is passed through inert gas, under inert gas shielding state, is warming up to 650 DEG C, after heat preservation carbonizes 4h with 6 DEG C/min rate program,
Continue to be warming up to 1550 DEG C, insulation reaction 5h with 10 DEG C/min rate program, obtains carbonized material, then carbonized material is protected in inert gas
Under shield state, 850 DEG C are cooled to the furnace, stopping is passed through inert gas, and moist dioxy is passed through into furnace with 300mL/min rate
Change carbon gas, after persistently fumigating 6h in humid carbon dioxide atmosphere, cool to room temperature with the furnace, discharge, obtains green body, then will
Gained green body is impregnated in the sodium hydroxide solution that mass fraction is 10%, and after ultrasonic immersing 45min, filtering is washed and dry,
Up to porous magnetic hydroxylapatite microballoon.The emulsifier is emulsifier op-10.The white oil is 40# white oil.The molysite
For ferric nitrate.The precipitating reagent is ammonium hydroxide.The inert gas is nitrogen.It is 5% that the humid carbon dioxide gas, which is moisture content,
Carbon dioxide gas.
In mass ratio be 1:10 by isoelectric point be 7.0 gelatin and water mix and pour into beaker, be stirred with glass bar
It is then 65 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred in standing swelling 8h under room temperature after 20min
40min is dissolved, it is cooling, obtain gelatin dispersion liquid, stand for standby use；According to parts by weight, 50 parts of gelatin dispersion liquids, 10 parts of creams are successively taken
Gelatin dispersion liquid is first preheated to 60 DEG C, and emulsifier is dissolved in the three-necked flask for filling white oil by agent, 60 parts of white oils,
The gelatin dispersion liquid after preheating is slowly added dropwise with 5mL/min rate to the white oil for having dissolved emulsifier by dropping funel again
In, the gelatin dispersion liquid after preheating is added dropwise, and three-necked flask is moved into ice-water bath, with blender with 500r/min revolving speed
Cooling and stirring 45min obtains No. 1 filter cake filter cake using filter, and by No. 1 filter cake vacuum freeze drying of gained, obtains gelatine microsphere；
In mass ratio be that 1:10 disperses gelatine microsphere in the iron salt solutions that mass fraction is 10%, in temperature be 6 DEG C, speed of agitator
Under the conditions of 500r/min, precipitating reagent is added, adjusts iron salt solutions pH to 8.5, after continuation low temperature is stirred to react 4h, filtering,
No. 2 filter cakes are obtained, and No. 2 filter cakes are washed with deionized 5 times, then No. 2 filter cakes after washing are transferred in vacuum freezing drying oven
It is dry, it obtains and once coats gelatine microsphere；According to parts by weight, 80 parts of primary cladding gelatine microspheres are successively taken, 30 parts of esters of silicon acis, 20
Part nanometer hydroxyapatite, 200 parts of water, first will once coat gelatine microsphere and water is added in reaction kettle, add nano-hydroxy
Apatite is then 50 DEG C in temperature, under the conditions of revolving speed is 800r/min, silicic acid is added dropwise into reaction kettle in constant temperature stirring
Ester continues constant temperature and is stirred to react 3h, filter, obtain No. 3 filter cakes, and institute will be washed with deionized after esters of silicon acis is added dropwise
No. 3 filter cake 3 times, then by No. 3 filter cake vacuum freeze dryings after washing, obtain secondary cladding microballoon；The secondary cladding of gained is micro-
Ball is transferred in retort, and inert gas is passed through into furnace with 500mL/min rate, under inert gas shielding state, with 6 DEG C/
Min rate program is warming up to 650 DEG C, after heat preservation carbonizes 4h, continues to be warming up to 1550 DEG C with 10 DEG C/min rate program, heat preservation is anti-
5h is answered, obtains carbonized material, then by carbonized material under inert gas shielding state, cools to 850 DEG C with the furnace, stopping is passed through indifferent gas
Body, and humid carbon dioxide gas is passed through into furnace with 300mL/min rate, it is persistently smoked in humid carbon dioxide atmosphere
After steaming 6h, room temperature is cooled to the furnace, discharge, obtain green body, then that gained green body is impregnated in the sodium hydroxide that mass fraction is 10% is molten
In liquid, after ultrasonic immersing 45min, filtering, washing and drying are to get porous magnetic hydroxylapatite microballoon.The emulsifier is
Emulsifier op-10.The white oil is 40# white oil.The molysite is ferric nitrate.The precipitating reagent is ammonium hydroxide.The esters of silicon acis is
Methyl orthosilicate.The inert gas is nitrogen.The humid carbon dioxide gas is the carbon dioxide gas that moisture content is 5%.
Comparative example: the porous magnetic hydroxylapatite microballoon of Wuxi new material Co., Ltd production.
Example 1 to the resulting porous magnetic hydroxylapatite microballoon of example 6 and comparative example product are subjected to performance detection, tool
Body detecting method is as follows:
The adsorption capacity (qe) and adsorption efficiency (η) calculation method of iron hydroxide are as follows:
Qe=(c0-ce) V/1000m (1)
η=(c0-ce)/c0 × 100% (2)
In formula: qe is the adsorbance of iron hydroxide, mg/g；V is the volume of solution, mL；M is the quality of test specimen, g；η is absorption
Efficiency, %.
Specific testing result is as shown in table 1:
The 1 specific testing result of porous magnetic hydroxylapatite microballoon of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example |
| Adsorbance/mg/g | 3.89 | 2.75 | 2.78 | 2.66 | 2.72 | 2.81 | 1.37 |
| Adsorption efficiency/% | 47.3 | 35.2 | 36.5 | 30.8 | 34.3 | 32.1 | 28.6 |
| Use adsorption efficiency/% after 96h | 45.5 | 27.3 | 25.7 | 22.9 | 17.7 | 16.4 | 10.7 |
By 1 testing result of table it is found that the porous magnetic hydroxylapatite microballoon of technical solution of the present invention preparation has excellent suction
The characteristics of attached performance and loading permanently effective holding, has wide in the development of porous adsorbing material technology of preparing industry
Prospect.
Claims (9)
1. a kind of preparation method of porous magnetic hydroxylapatite microballoon, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 30~50 parts of gelatin dispersion liquids, 8~10 parts of emulsifiers are successively taken, 40~60 parts of white oils first will
The preheating of gelatin dispersion liquid, and emulsifier is dissolved in white oil, then the gelatin dispersion liquid after preheating is slowly added dropwise to dissolution
In the white oil of emulsifier, the gelatin dispersion liquid after preheating is added dropwise, cooling and stirring, is filtered, dry, obtains gelatine microsphere；
(2) it in mass ratio disperses gelatine microsphere in iron salt solutions for 1:5~1:10, under the conditions of temperature is 4~6 DEG C, then
Precipitating reagent is added, adjusts iron salt solutions pH to 8.0~8.5, and the dopamine of iron salt solutions quality 1~2% is added, continues low temperature
After being stirred to react 2~4h, filtering washs and dry, obtains and once coat gelatine microsphere；
(3) according to parts by weight, 60~80 parts of primary cladding gelatine microspheres are successively taken, 20~30 parts of esters of silicon acis, 10~20 parts are received
Primary cladding gelatine microsphere is first dispersed in water, adds nano-hydroxy-apatite by rice hydroxyapatite, 100~200 parts of water
Then esters of silicon acis is added dropwise under constant temperature stirring in stone, after being added dropwise, continues constant temperature and is stirred to react, filter, washs and dry
It is dry, obtain secondary cladding microballoon；
(4) by the secondary cladding microballoon of gained under inert gas shielding state, heating charing, then further heat up to 1500~
1550 DEG C, insulation reaction obtains carbonized material；
(5) by carbonized material under the conditions of 800~850 DEG C, after persistently fumigating 4~6h in humid carbon dioxide atmosphere, out
Material, alkali leaching, washing are dry to get porous magnetic hydroxylapatite microballoon.
2. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(1) it is that 1:8~1:10 is formulated that the gelatin dispersion liquid is by gelatin and water in mass ratio.
3. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(1) emulsifier is emulsifier op-10, any one in Tween-60 or Si Pan -80.
4. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(1) white oil is any one in 40# white oil, 45# white oil or 50# white oil.
5. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(2) molysite is any one in ferric nitrate, iron chloride or ferric sulfate.
6. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(2) precipitating reagent is any one in ammonium hydroxide or urea.
7. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(3) esters of silicon acis is any one in methyl orthosilicate, ethyl orthosilicate or positive silicic acid propyl ester.
8. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(4) inert gas is any one in nitrogen, helium or argon gas.
9. a kind of preparation method of porous magnetic hydroxylapatite microballoon according to claim 1, it is characterised in that step
(5) the humid carbon dioxide gas is the carbon dioxide gas that moisture content is 3~5%.
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