CN105126770A - Preparation method of pectin core-shell-structured microsphere adsorption material - Google Patents
Preparation method of pectin core-shell-structured microsphere adsorption material Download PDFInfo
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Abstract
The invention discloses a preparation method of a pectin core-shell-structured microsphere adsorption material, wherein the method includes the steps of 1) preparing metal oxide powder; 2) preparing a metal oxide solution and a pectin solution, wherein the pectin solution is a shell layer solution; 3) mixing the pectin solution, the metal oxide solution and a dispersion agent B according to the weight ratio of 1:6:3 to form a core layer solution; 4) respectively injecting the shell layer solution and the core layer solution into an outer layer and an inner layer of a stainless steel co-axial injector head; 5) ejecting the shell layer solution and the core layer solution into a receiving apparatus through a high-voltage electrostatic spinning device under a high-voltage electrostatic ejection condition, and stirring and filtering the solutions; 6) soaking the microspheres in a metal salt solution, and stirring, filtering and drying the mixture to prepare the core-shell-structured microsphere adsorption material. The core-shell-structured microsphere has excellent adsorption performance, can be widely used in negative ion separation, such as fluorine ion and the like, and waste water treatment, and is easy to treat after being used, is free of secondary pollution and has important significance on environment protection.
Description
Technical field
The invention belongs to biomass economy and sorbing material technical field, be specifically related to the preparation of a kind of pectin-pectin/metal oxide nucleocapsid structure micro-sphere absorption material.
Background technology
Fluorine is one of trace element of needed by human, and appropriate fluorine is the necessary guarantee of human skeletal and dental health growth, and excessive fluorine will cause fluorine poisoning, den tal fluorosis, and fluorosis of bone.Fluorine waste water is mainly derived from mining, metal smelt, production of phosphate fertilizer, nuclear leakage and uranium ore processing, when these emissions enter into underground water, and the health affecting human body that can be serious.There is various technology both at home and abroad to process fluoride waste now, such as: chemical precipitation method, ion-exchange, electrodialysis, counter-infiltration, Donnan dialysis, coagulation sedimentation, absorption etc., wherein absorption method is used widely because technique is simple, clearance is high, stable water outlet, expense are low.The key that absorption method removes fluorine is the adsorbent that preparation is efficient, economy and environment is friendly.Metal oxide powder is as Al
2o
3, ZrO
2itself have good fluorine ion adsorption capacity, Chang Zuowei adsorbent is used for except fluorine, but powder sorbent exists separation difficulty, and upper prop difficulty, the discarded post processing difficulty of use, easily cause secondary pollution problems.Therefore, seek a kind of adsorption efficiency high, can repeatedly reuse, low cost, easily reclaim, easily process, sorbing material simple to operate
Pectin is a kind of natural polysaccharide compounds.Pectin is water-soluble and be insoluble to organic solvent, electronegative, its mid-molecule divides carboxyl by methanol esterification, according to the difference of esterification degree (DE), DE is greater than 50% be called HM (also claiming high-ester pectin), be less than 50% be called LM (also claiming low-ester pectin), and the characteristic of esterification degree to pectin has a great impact, especially gel strength and solubility.The pectin of different esterification degree has different gel mechanism, and high-ester pectin needs to form gel under the sugared low pH condition of height; Low-ester pectin at polyvalent metal ion as Ca
2+, Fe
3+, La
3+, Al
3+, Zr
4+etc. gel just can be formed when existing, form so-called " egg carton " structure.According to hsab theory, Ca
2+, Fe
3+, La
3+, Al
3+, Zr
4+belong to hard acid ion Deng polyvalent metal ion, these hard acid ions easily and F
-, OH
-, PO
4 3-, SO
4 2-, ClO
4 -, NO
3 -deng hard base ions binding, so, pectin and polyvalent metal ion are reacted the gel with " egg carton " structure being formed and have cured a large amount of hard acid ion, can be used as F
-deng anion adsorbent.Pectin-pectin/metal oxide nucleocapsid structure microballoon, because in microballoon shell, pectin surface have cured a large amount of hard acid metal ion be easily combined with fluorine ion, metal oxide in the stratum nucleare of simultaneously microballoon can react with fluorine ion again, stratum nucleare and the common effect of shell, to greatly increase the adsorption capacity of microballoon, improve adsorption efficiency.If directly metal oxide powder is made with pectin and mixes microballoon, easily there is the problem that the metal oxide powder in microballoon drops in use, and the pectin/metal oxide microspheres of nucleocapsid structure, metal oxide is stratum nucleare, gelatin is shell, avoids the problem that powder drops.Solve metal oxide powder separation difficulty, the problems such as upper prop is difficult, post processing is difficult, turn improve intensity and the adsorbance of microballoon simultaneously.This sorbing material can be widely used in adsorbing separation and the wastewater treatment of the anion such as the field such as chemical industry and environmental protection fluorine ion.The microballoon of nucleocapsid structure, main component is pectin, and pectin is a kind of polysaccharide, and have the features such as biodegradable, easily disposal, after microsphere adsorbing agent uses, renewable, recycling, easily reclaims, easily disposes, and can not cause secondary pollution to environment.
The preparation method of present nucleocapsid structure microballoon mainly contains seeded polymerization, macromonomer method, self-assembly method, progressively heterocoagulation method etc., generally all there is the problems such as reactions steps is many, preparation process is complicated, grade sized microspheres is not easily prepared in these methods, such as progressively heterocoagulation method wastes time and energy at polyelectrolyte deposition and purge process, and polyelectrolyte is often introduced in shell; The selection of macromonomer method to the design of monomer molecule and copolyreaction condition requires higher.Compared with these methods, it is a kind of simple and easy method obtaining core-shell particles that coaxial electrostatic sprays.Coaxial electrostatic spraying technique is improved on common electrostatic injection apparatus basis, the different shower nozzle of two coaxial sizes is connected with in injector tip, interior nozzle set is outside in shower nozzle, stratum nucleare solution sprays from interior shower nozzle, shell solution sprays from outer shower nozzle, make the liquid objectionable intermingling of shell and stratum nucleare and can spray simultaneously, the nucleocapsid structure be separated completely can be kept.Coaxial electrical spray prepares nucleocapsid structure microballoon, has the advantages such as microballoon size can control, easy and simple to handle, preparation process environmental friendliness.Such as patent document CN104707575A discloses " a kind of preparation method of magnetic core-shell alginate microsphere adsorbent ", this patent document has prepared by coaxial electrostatic injection method the Core-shell magnetic composite microspheres take sodium alginate as shell, sodium alginate and nano ferriferrous oxide being stratum nucleare, and by the absorption of this Core-shell magnetic composite microspheres application with fluorine ion, but its adsorbance is lower than 15mg/g, can not meets and the removal of fluorine ion is applied.
Summary of the invention
As the result of various extensive and careful research and experiment, the adsorbance of core-shell particles to fluorine ion that it be shell, pectin and slaine is stratum nucleare that the present inventor has been found that with pectin is higher, based on this discovery, completes the present invention.
An object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
A further object of the invention is by coaxial electrostatic injection method, arranging certain nozzle parameter is ejected in metal salt solution by solution, prepare the core-shell particles take pectin as shell, pectin and slaine being stratum nucleare, the metal ion that pectin layer have cured easily and fluorine ion reacts of this microballoon shell layer surface, in stratum nucleare, metal oxide can react with fluorine ion again, under the effect that both are common, obtain higher adsorption efficiency, in stratum nucleare, metal oxide improves the compression strength of pectin microballoon simultaneously.
In order to realize, according to these objects of the present invention and other advantage, providing the preparation method of a kind of pectin/metal oxide nucleocapsid structure micro-sphere absorption material, comprise the following steps:
Step one, the slaine A of 1-5 weight portion added in the water of 20-100 weight portion mix, then adding alkaline solution adjust ph is 7-12, stir and add dispersant A after 1-3 hour, continue stirring 0.5 ~ 1.5 hour, then centrifugal 3-5 time, by the centrifugal solid freeze drying 20-24h obtained, finally at 500-1200 DEG C, calcine 1-3 hour with Muffle furnace, obtain metal oxide powder, then getting metal oxide powder adds in deionized water, stirs and obtains the metal oxide solution of 0.1-1wt%; Described dispersant A is the one in lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide; The addition of described dispersant A is the 3-5% of slaine A weight;
Step 2, pectin is added in deionized water, stir and make it dissolve completely, obtain the pectin solution that concentration is 1-10wt%, i.e. shell solution;
Metal oxide solution prepared by step 3, pectin solution step 2 prepared, step one and dispersant B are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described dispersant B is 3-5wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, and to set environment temperature in electrostatic spinning machine be 10-35 DEG C, the output voltage of high voltage source is 3-8kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 5-10cm, the flow velocity of stratum nucleare solution and shell solution is 0.5-2.0mL/h, the velocity ratio 1:2-1:4 of stratum nucleare solution and shell solution, ambient humidity 25-30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of 6 ~ 8wt% calcium chloride solution, stir with 150-250r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the slaine B solution of 1-5wt%, stirs 2-5 hour with the speed of 150 ~ 250r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
Preferably, described slaine A is AlCl
36H
2o, Zr (NO
3)
45H
2o, Ce (NO
3)
3, Fe
2(SO
4)
3in the combination of one or more; Described metal oxide is Al
2o
3, ZrO
2, CeO
2, Fe
2o
3the combination of one or more.
Preferably, described slaine A is by AlCl
36H
2o and Zr (NO
3)
45H
2during O combination, its mol ratio by Al and Zr is 1:4 mixing composition; Described slaine A is by Ce (NO
3)
3with Zr (NO
3)
45H
2during O combination, its mol ratio by Ce and Zr is 1:3 mixing composition; Described slaine A is by Fe
2(SO
4)
3with Zr (NO
3)
45H
2during O combination, its mol ratio by Fe and Zr is 1:2 mixing composition.
Preferably, described alkaline solution is the one in sodium hydroxide solution and/or urea liquid; The concentration of described alkaline solution is 5-10mol/L.
Preferably, described pectin is the low-ester pectin of esterification degree within the scope of 30%-40%.
Preferably, described dispersant B is the one in carrene, dichloroethanes, chloroform.
Preferably, described slaine B solution is the one in lanthanum chloride, calcium chloride, aluminium chloride and zirconium nitrate solution.
Preferably, the average diameter of the micro-sphere absorption material of described nucleocapsid structure is 0.8-1.5mm, and wherein stratum nucleare thickness is 0.2-0.6mm, and shell thickness is 0.6-0.9mm.
Preferably, in described step 4, calcium chloride solution can be substituted by the mixed solution of calcium chloride and strontium chloride, and calcium chloride and strontium chloride mix by weight 1:1 ~ 3.
Preferably, after adding dispersant A in described step one, continue can to add ultrasonic wave in the stirring process of 0.5 ~ 1.5 hour and disperse, described hyperacoustic frequency is 10 ~ 20KHz; In described step 3, the preparation of mixed solution can add ultrasonic wave and mixes, and described hyperacoustic frequency is 10 ~ 20KHz, and described ultrasonic time is 1 ~ 2 hour.
Adding alkaline solution in step one of the present invention regulates the object of pH to be make solution alkaline, makes metal salt solution complete reaction generate precipitation; The pelleting centrifugation generated 3 ~ 5 times, concrete centrifugal method is: centrifugally once centrifugate toppled over afterwards, then rejoining water carries out centrifugal, repeat 3 ~ 5 times, the object done like this is because add as alkaline solution as sodium hydroxide solution may form the crystallization of sodium chloride, repeatedly centrifugal is to be removed by sodium chloride, obtaining pure precipitation.
In step one of the present invention dispersant A add the precipitation of generation can be made to disperse more even, the granular size of formation is more evenly and can prevent the reunion of particle from occurring.
The concentration of the pectin adopted in step one of the present invention is 1-10wt%, due to the present invention's employing is coaxial electrical spraying technique, at this concentration, EFI pectin solution can form stable particulate, if concentration is lower than this scope, then pectin solution is not easy EFI balling-up, if higher than this scope, then in EFI process, easily blocks shower nozzle.
Metal oxide solution prepared by pectin solution step 2 prepared in step 3 of the present invention, step one and dispersant B are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution, by the metai oxide curing problem that can overcome the rear difficult separation of metal oxide powder absorption, difficult upper prop in pectin, add dispersant B, dispersant B is the one in organic solvent dichloromethane, dichloroethanes, chloroform simultaneously, pectin solution and metal oxide dispersion can effectively mix by dispersant B on the one hand, dispersant B can play the effect of solvent on the other hand, stratum nucleare is made to form organic phase, different with the SOLUTION PROPERTIES of shell, make the solution objectionable intermingling of shell and stratum nucleare, and adopt dispersant B concentration to be 3-5wt%, at this concentration, stable core-shell particle can be formed in coaxial electrostatic course of injection, if lower than this scope, then organic phase is not enough, nucleocapsid solution is easily caused mutually to dissolve, if higher than this scope, then organic phase concentration is too high, easily shower nozzle is blocked in EFI process.
In step 3 of the present invention, the concentration of metal oxide is 0.1-1wt%, at this concentration, the absorption property of the core-shell particle that EFI obtains to fluorine ion is higher, if lower than this scope, the absorption property of the core-shell particles then obtained to fluorine ion is poor, if higher than this scope, then in EFI process, easily block shower nozzle.
The high-pressure electrostatic spraying equipment adopted in step 4 of the present invention, two boost pumps are equipped with, the syringe put into respectively on pump and stratum nucleare solution and shell solution are housed is pushed away at two, by controlling the fltting speed of boost pump, shell solution and stratum nucleare solution are input to respectively skin and the internal layer of stainless steel Coaxial nozzle, in stainless steel Coaxial nozzle, voltage is applied by high-pressure electrostatic output equipment, and the jet of receiving system and Coaxial nozzle is arranged certain spacing, injection obtains core-shell particles, high-pressure electrostatic injection conditions is in the present invention: environment temperature is 10-35 DEG C, the output voltage of high voltage source is 3-8kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 5-10cm, flow is 0.5-2mL/h, the velocity ratio of stratum nucleare solution and shell solution is 1:2-1:4, ambient humidity 25-30%, under this EFI condition, advantages of good adsorption effect can be formed, the obvious particulate of nucleocapsid structure, when temperature is lower than 10 DEG C, solution may be caused by mobility step-down, cause the blocking of spinning nozzle, when temperature is more than 35 DEG C, the too high volatilization causing solution internal solvent of temperature, affects the structure of microballoon, when voltage is lower than 3kV, electric field force is too small, cause the bulk deposition of coaxial spinning nozzle colloidal sol and can not spray fast, cause the diameter obtaining microballoon excessive, when voltage is greater than 8kV, electric field force is excessive, causes the ejection scope of colloidal sol to become large, effectively can not collect microballoon, the form of microballoon may be caused to become thread simultaneously, when distance between receiving system and spinning nozzle is lower than 5cm, cause the electric field force between spinning nozzle and gathering-device excessive, the form of microballoon is caused to become thread, when distance is more than 10cm, electric field force is too small, cause spinning nozzle colloidal sol not spray fast and to pile up, cause the diameter obtaining microballoon excessive, when flow velocity is lower than 0.5mL/h, the spray volume of solution is less, the quantity of electric charge that solution carries is less, therefore the microballoon amount that obtains within the unit interval of solution is less, the efficiency of impact preparation, when flow velocity is greater than 2mL/h, a large amount of solution is ejected, the microsphere diameter formed is comparatively large, easily causes spinning nozzle to be blocked by solution when flow velocity is excessive simultaneously, when the velocity ratio of stratum nucleare solution and shell solution is lower than 1:2 ~ 1:4, shell solution can not effectively comprise stratum nucleare solution, the nucleocapsid structure of structural integrity can not be formed, when velocity ratio is higher than 1:2 ~ 1:4, the amount of stratum nucleare solution is lower than the amount of shell solution, the adsorption effect of particulate to fluorine ion of the nucleocapsid structure obtained is poor, can not meet the demands.
In step 4 of the present invention, the size of preferred stainless steel Coaxial nozzle is No. 4 ~ 6, interior shower nozzle, No. 8 ~ 12, outer shower nozzle, the size of shower nozzle determines the diameter of microballoon to a certain extent, when interior shower nozzle is less than 4 ~ 6, easily cause the blocking of spinning nozzle, when outer shower nozzle is greater than 8 ~ No. 12, the solution spray volume of shower nozzle is excessive, is not easy to form the uniform micro-sphere structure of form.
The pectin adopted in the present invention is the low-ester pectin of esterification degree within the scope of 30%-40%, low-ester pectin at polyvalent metal ion as Ca
2+, Fe
3+, La
3+, Al
3+, Zr
4+etc. gel just can be formed when existing, form so-called " egg carton " structure.According to hsab theory, Ca
2+, Fe
3+, La
3+, Al
3+, Zr
4+belong to hard acid ion Deng polyvalent metal ion, these hard acid ions easily and F
-, OH
-, PO
4 3-, SO
4 2-, ClO
4 -, NO
3 -deng hard base ions binding, so, pectin and polyvalent metal ion are reacted the gel with " egg carton " structure being formed and have cured a large amount of hard acid ion, can be used as F
-deng anion adsorbent.
In step 4 of the present invention, the microballoon of preparation is immersed in slaine B, hard acid metal ion in slaine B can be solidificated in the surface of pectin in microballoon shell by this process, hard acid metal ion can be combined the effect playing Adsorption of fluoride ion with fluorine ion, metal oxide in the stratum nucleare of simultaneously microballoon can react with fluorine ion again, stratum nucleare and the common effect of shell, to greatly increase the adsorption capacity of microballoon, improve adsorption efficiency.
The present invention at least comprises following beneficial effect:
(1) the present invention with pectin, metal oxide for primary raw material.Al
2o
3, ZrO
2, CeO
2, Fe
2o
3etc. advantages of good adsorption effect, but there is separation, upper prop difficulty in powder sorbent, is made into the problem that microballoon overcomes powder separation difficulty, difficult upper prop.Pectin has the feature of biodegradability, and after microsphere adsorbing agent uses, renewable, recycling, easily reclaims, easily disposes, can not cause secondary pollution to environment.
(2) pectin-pectin/metal oxide nucleocapsid structure microballoon is prepared by coaxial electrical spray technique, because of the metal ion that microballoon shell layer surface pectin layer have cured easily and fluorine ion reacts, in stratum nucleare, metal oxide can react with fluorine ion again, under the effect that both are common, obtain higher adsorption efficiency, in stratum nucleare, metal oxide improves the compression strength of pectin microballoon simultaneously.Pectin-pectin/metal oxide nucleocapsid structure microballoon, as sorbing material or separation and concentration material, can be widely used in adsorbing separation and the wastewater treatment of the field such as chemical industry and environmental protection fluorine ion.
(3) size of pectin-pectin of the present invention/metal oxide nucleocapsid structure microballoon controls by the size controlling the size of injection showerhead, flow velocity size and voltage, obtains the microballoon of different-diameter size.
(4) preparation method of the present invention is simple to operate, and efficiency is high, preparation process environmental friendliness, practical, the abundant raw material source of adsorbent, and cost is low, and made adsorbent is a kind of environment-friendly material.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Accompanying drawing illustrates:
Fig. 1 is the easy device figure of the coaxial electrostatic injection method adopted in the present invention;
Wherein, 1, shell syringe, 2, stratum nucleare syringe, 3, high voltage source; 4, agitator; 5, receiving system;
Fig. 2 is the scanning electron microscope (SEM) photograph of core-shell particles prepared by the embodiment of the present invention 1;
Fig. 3 is the surface sweeping Electronic Speculum figure of core-shell particles section prepared by the embodiment of the present invention 1;
Fig. 4 is the absorption figure of core-shell particles under different pH prepared by the embodiment of the present invention 1.
Detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to description word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
Embodiment 1:
Step one, by slaine AlCl
36H
2o and Zr (NO
3)
45H
2o is 1:4 mixing by the mol ratio of Al and Zr, then get the mixed metal salt of 1 weight portion to add in the water of 20 weight portions and mix, then the sodium hydroxide solution adjust ph adding 6mol/L is 8-8.5, stir and add dispersant A after 3 hours, continue stirring 0.5 hour, then centrifugal 3 times, by the centrifugal solid freeze drying 24h obtained, finally calcine 1 hour at 700 DEG C with Muffle furnace, obtain metal oxide Al
2o
3-ZrO
2powder, then gets Al
2o
3-ZrO
2powder adds in deionized water, stirs and obtains the Al of 1wt%
2o
3-ZrO
2solution; Described dispersant A is lauryl sodium sulfate; The addition of described dispersant A is 3% of mixed metal salt A weight;
Step 2, pectin is added in deionized water, stir 3h and make it dissolve completely, obtain the pectin solution that concentration is 6wt%, i.e. shell solution;
Al prepared by step 3, pectin solution step 2 prepared, step one
2o
3-ZrO
2solution and carrene are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described carrene is 3wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, the size of described stainless steel Coaxial nozzle is No. 4, interior shower nozzle, No. 8, outer shower nozzle, and to set environment temperature in electrostatic spinning machine be 30 DEG C, the output voltage of high voltage source is 3kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 8cm, the flow velocity of stratum nucleare solution is 0.5mL/h, the flow velocity of shell solution is 1mL/h, ambient humidity 25%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of 6wt% calcium chloride solution, stir with 150r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the liquor alumini chloridi of 2wt%, stirs 2 hours with the speed of 150r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure, figure Fig. 2 is the scanning electron microscope (SEM) photograph of core-shell particles prepared by the present embodiment, Fig. 3 is the surface sweeping Electronic Speculum figure of core-shell particles section prepared by the present embodiment, as can be seen from the figure the microballoon prepared has obvious nucleocapsid structure.
Embodiment 2:
Step one, by slaine Ce (NO
3)
3with Zr (NO
3)
45H
2o is 1:3 mixing by the mol ratio of Ce and Zr, then get the mixed metal salt of 2 weight portions to add in the water of 50 weight portions and mix, then the urea liquid adjust ph adding 6mol/L is 8-8.5, stir and add dispersant A after 3 hours, continue stirring 1 hour, then centrifugal 5 times, by the centrifugal solid freeze drying 24h obtained, finally calcine 2 hours at 800 DEG C with Muffle furnace, obtain metal oxide CeO
2-ZrO
2powder, then gets CeO
2-ZrO
2powder adds in deionized water, stirs and obtains the CeO of 1wt%
2-ZrO
2solution; Described dispersant A is methyl anyl alcohol; The addition of described dispersant A is 5% of mixed metal salt A weight;
Step 2, pectin is added in deionized water, stir 3h and make it dissolve completely, obtain the pectin solution that concentration is 5wt%, i.e. shell solution;
CeO prepared by step 3, pectin solution step 2 prepared, step one
2-ZrO
2solution and carrene are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described carrene is 5wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, the size of stainless steel Coaxial nozzle is No. 5, interior shower nozzle, No. 10, outer shower nozzle, and to set environment temperature in electrostatic spinning machine be 30 DEG C, the output voltage of high voltage source is 5kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 6cm, the flow velocity of stratum nucleare solution is 1mL/h, the flow velocity of shell solution is 2mL/h, ambient humidity 30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of the mixed solution of 6wt% calcium chloride and strontium chloride, stir with 150r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the liquor alumini chloridi of 2wt%, stirs 2 hours with the speed of 150r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
Embodiment 3:
Step one, by 3 weight portion Zr (NO
3)
45H
2o adds in the water of 80 weight portions and mixes, the mixed solution adjust ph of the NaOH and urea that then add 6mol/L is 8-8.5, stir and add dispersant A after 3 hours, continue stirring 1 hour, then centrifugal 4 times, by the centrifugal solid freeze drying 24h obtained, finally calcine 2 hours at 700 DEG C with Muffle furnace, obtain metal oxide ZrO
2powder, then gets ZrO
2powder adds in deionized water, stirs and obtains the ZrO of 1wt%
2solution; Described dispersant A is methyl anyl alcohol; The addition of described dispersant A is 5% of mixed metal salt A weight;
Step 2, pectin is added in deionized water, stir 3h and make it dissolve completely, obtain the pectin solution that concentration is 6wt%, i.e. shell solution;
ZrO prepared by step 3, pectin solution step 2 prepared, step one
2solution and chloroform are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described chloroform is 5wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, the size of stainless steel Coaxial nozzle is No. 6, interior shower nozzle, No. 12, outer shower nozzle, and to set environment temperature in electrostatic spinning machine be 25 DEG C, the output voltage of high voltage source is 5kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 5cm, the flow velocity of stratum nucleare solution is 0.5mL/h, the flow velocity of shell solution is 1.5mL/h, ambient humidity 30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of the mixed solution of 6wt% calcium chloride and strontium chloride, stir with 150r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the lanthanum chloride solution of 3wt%, stirs 5 hours with the speed of 200r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
Embodiment 4:
Step one, by slaine Fe
2(SO
4)
3with Zr (NO
3)
45H
2o is 1:2 mixing by the mol ratio of Fe and Zr, then get the mixed metal salt of 5 weight portions to add in the water of 100 weight portions and mix, then the sodium hydroxide solution adjust ph adding 6mol/L is 8-8.5, stir and add dispersant A after 3 hours, continue stirring 1 hour, then centrifugal 5 times, by the centrifugal solid freeze drying 24h obtained, finally calcine 3 hours at 600 DEG C with Muffle furnace, obtain metal oxide Fe
2o
3-ZrO
2powder, then gets Fe
2o
3-ZrO
2powder adds in deionized water, stirs and obtains the Fe of 1wt%
2o
3-ZrO
2solution; Described dispersant A is polyacrylamide; The addition of described dispersant A is 5% of mixed metal salt A weight;
Step 2, pectin is added in deionized water, stir 3h and make it dissolve completely, obtain the pectin solution that concentration is 7wt%, i.e. shell solution;
Fe prepared by step 3, pectin solution step 2 prepared, step one
2o
3-ZrO
2solution and dichloroethanes are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described dichloroethanes is 4wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, the size of stainless steel Coaxial nozzle is No. 5, interior shower nozzle, No. 12, outer shower nozzle, and to set environment temperature in electrostatic spinning machine be 35 DEG C, the output voltage of high voltage source is 8kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 10cm, the flow velocity of stratum nucleare solution is 1mL/h, the flow velocity of shell solution is 2mL/h, ambient humidity 30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of the mixed solution of 6wt% calcium chloride and strontium chloride, stir with 150r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the lanthanum chloride solution of 2wt%, stirs 2 hours with the speed of 150r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
Embodiment 5:
Step one, by slaine Fe
2(SO
4)
3with Zr (NO
3)
45H
2o is 1:2 mixing by the mol ratio of Fe and Zr, then get the mixed metal salt of 2 weight portions to add in the water of 20 weight portions and mix, then the urea liquid adjust ph adding 6mol/L is 8-8.5, stir and add dispersant A after 2 hours, and solution inserted ultrasonic in ultrasonic disperse equipment and continue stirring 1 hour, then centrifugal 3 times, by the centrifugal solid freeze drying 24h obtained, finally calcine 3 hours at 800 DEG C with Muffle furnace, obtain metal oxide Fe
2o
3-ZrO
2powder, then gets Fe
2o
3-ZrO
2powder adds in deionized water, stirs and obtains the Fe of 0.8wt%
2o
3-ZrO
2solution; Described dispersant A is polyacrylamide; The addition of described dispersant A is 5% of mixed metal salt A weight; Described hyperacoustic frequency is 15KHz;
Step 2, pectin is added in deionized water, stir 3h and make it dissolve completely, obtain the pectin solution that concentration is 10wt%, i.e. shell solution;
Fe prepared by step 3, pectin solution step 2 prepared, step one
2o
3-ZrO
2solution and dichloroethanes are by weight 1:6:3 mixing, and juxtaposition to enter in ultrasonic dispersing apparatus ultrasonic 2 hours, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described dichloroethanes is 5wt%; Described hyperacoustic frequency is 15KHz;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, the size of stainless steel Coaxial nozzle is No. 4, interior shower nozzle, No. 10, outer shower nozzle, and to set environment temperature in electrostatic spinning machine be 30 DEG C, the output voltage of high voltage source is 4kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 8cm, the flow velocity of stratum nucleare solution is 1mL/h, the flow velocity of shell solution is 2mL/h, ambient humidity 30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of the mixed solution of 7wt% calcium chloride and strontium chloride, stir with 150r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the lanthanum chloride solution of 3wt%, stirs 2 hours with the speed of 150r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
In order to effect of the present invention is described, inventor provides contrast experiment as follows:
Comparative example 1:
In step one of the present invention, the concentration of the metal oxide solution of preparation is 0.08wt%, and identical with in embodiment 1 of all the other parameters, technical process is also identical.
Comparative example 2:
In step one of the present invention, the concentration of the metal oxide solution of preparation is 1.2wt%, and identical with in embodiment 1 of all the other parameters, technical process is also identical.
Comparative example 3:
In step 2 of the present invention, the concentration of the pectin solution of preparation is 0.8wt%, and identical with in embodiment 2 of all the other parameters, technical process is also identical.
Comparative example 4:
In step 2 of the present invention, the concentration of the pectin solution of preparation is 11wt%, and identical with in embodiment 2 of all the other parameters, technical process is also identical.
Comparative example 5:
In step 4 of the present invention, the concentration of slaine B solution is 0.8wt%, and identical with in embodiment 3 of all the other parameters, technical process is also identical.
Comparative example 6:
In step 4 of the present invention, the concentration of slaine B solution is 5.5wt%, and identical with in embodiment 4 of all the other parameters, technical process is also identical.
The micro-sphere absorption material of the nucleocapsid structure adopting above embodiment 1-5 and comparative example 1-6 to prepare carries out Static Adsorption research to fluoride solution respectively.
Fig. 4 is that the micro-sphere absorption material of the nucleocapsid structure of preparation in the embodiment of the present invention 1 is to the adsorption effect figure of the fluoride solution of different pH, experimentation is: the Fluorinse mixing of getting adsorbent 0.05g and 50mL100mg/L, pH is regulated to be 2,4,6,8,10 respectively, be placed in shaking table vibration 24h, rotating speed is 130rpm, and adsorption temp is 25 DEG C; Record fluorinion concentration in the solution of absorption front and back with fluoride ion electrode, and calculate adsorbance, as shown in Figure 4, illustrate that the adsorbance of adsorbent is maximum when pH is 4.
Get the Fluorinse mixing of micro-sphere absorption material 0.05g and the 50mL100mg/L of nucleocapsid structure prepared by above-described embodiment 1-5 and comparative example 1-6 respectively, regulate pH to be 4, be placed in shaking table vibration 24h, rotating speed is 130rpm, and adsorption temp is 25 DEG C; Fluorinion concentration in the solution of absorption front and back is recorded with fluoride ion electrode;
See the adsorption effect of fluorine ion is as shown in table 1, the adsorbance of sorbing material is calculated by following formula (2),
Adsorbance=(Co-Ce) V/m (2)
Wherein, Co is the concentration of fluorine ion before absorption, and Ce is the concentration of fluorine ion after adsorption equilibrium, and V is the volume adding fluoride solution, and m is the quality of the micro-sphere absorption material of the nucleocapsid structure added.
Table 1
| Adsorbance | |
| Embodiment 1 | 45.2mg/g |
| Embodiment 2 | 46.5mg/g |
| Embodiment 3 | 44.8mg/g |
| Embodiment 4 | 45.5mg/g |
| Embodiment 5 | 47.5mg/g |
| Comparative example 1 | 35.2mg/g |
| Comparative example 2 | 46.2mg/g |
| Comparative example 3 | 36.4mg/g |
| Comparative example 4 | 46.8mg/g |
| Comparative example 5 | 36.8mg/g |
| Comparative example 6 | 44.9mg/g |
As known from Table 1, embodiment 1-5 have employed raw material in proportion of the present invention and technological parameter, and it is better to the adsorption effect of fluoride solution, is all greater than 44mg/g to the adsorbance of fluorine ion.
The concentration of the metal oxide solution that comparative example 1 and comparative example 2 are prepared in step one is not in scope of the present invention, and comparative example 1 is lower than this scope, and the content of the metal oxide in the stratum nucleare of microballoon is lower, poor to the adsorption effect of fluorine ion; Comparative example 2 is higher than this scope, although the material prepared higher than embodiment 1 adsorption effect of fluorine ion, occurs the phenomenon of blocking shower nozzle, be unfavorable for the preparation of core-shell particles in the process of EFI
The concentration of the pectin solution that comparative example 3 and comparative example 4 are prepared in step 2 is not in scope of the present invention, comparative example 3 is lower than this scope, in the process of EFI, pectin solution is not easy balling-up, and the content of pectin is lower, cause the content of the slaine B ion combined also lower, so poor to the adsorption effect of fluorine ion; Comparative example 4 is higher than this scope, although the material prepared higher than embodiment 2 adsorption effect of fluorine ion, occurs the phenomenon of blocking shower nozzle, be unfavorable for the preparation of core-shell particle in EFI process.
The concentration of the slaine B that comparative example 5 and comparative example 6 use in step 4 is not in scope of the present invention, comparative example 5 is lower than this scope, cause core-shell particles can not be complete with the metal ion commissure in slaine B solution, adsorption effect is low, comparative example 6 is higher than this scope, metal ion then in core-shell particles and slaine B solution is crosslinked to reach capacity, and can not improve adsorption effect significantly.
Visible, the raw material adopted in the present invention is in described ratio, and in the preparation process of sorbing material, parameters is in described scope, and the absorption property of sorbing material to fluorine ion of preparation is better.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1. a preparation method for pectin nucleocapsid structure micro-sphere absorption material, is characterized in that, comprises the following steps:
Step one, the slaine A of 1-5 weight portion added in the water of 20-100 weight portion mix, then adding alkaline solution adjust ph is 7-12, stir and add dispersant A after 1-3 hour, continue stirring 0.5 ~ 1.5 hour, then centrifugal 3-5 time, by the centrifugal solid freeze drying 20-24h obtained, finally at 500-1200 DEG C, calcine 1-3 hour with Muffle furnace, obtain metal oxide powder, then getting metal oxide powder adds in deionized water, stirs and obtains the metal oxide solution of 0.1-1wt%; Described dispersant A is the one in lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide; The addition of described dispersant A is the 3-5% of slaine A weight;
Step 2, pectin is added in deionized water, stir and make it dissolve completely, obtain the pectin solution that concentration is 1-10wt%, i.e. shell solution;
Metal oxide solution prepared by step 3, pectin solution step 2 prepared, step one and dispersant B are by weight 1:6:3 mixing, and stir to obtain mixed solution, i.e. stratum nucleare solution; The concentration of described dispersant B is 3-5wt%;
Step 4, above-mentioned stratum nucleare solution and shell solution are injected into respectively internal layer and the skin of stainless steel Coaxial nozzle in electrostatic spinning machine, and to set environment temperature in electrostatic spinning machine be 10-35 DEG C, the output voltage of high voltage source is 3-8kv, distance between receiving system and stainless steel Coaxial nozzle spinning nozzle is 5-10cm, the flow velocity of stratum nucleare solution and shell solution is 0.5-2.0mL/h, the velocity ratio 1:2-1:4 of stratum nucleare solution and shell solution, ambient humidity 25-30%, then shell solution and stratum nucleare solution being ejected under above-mentioned high-pressure electrostatic injection conditions and filling concentration is in the receiving system of 6-8wt% calcium chloride solution, stir with 150-250r/min, filter, obtain microspheres with solid, microspheres with solid being immersed in concentration is in the slaine B solution of 1-5wt%, stirs 2-5 hour with the speed of 150-250r/min, filters, and dries, obtains the micro-sphere absorption material of nucleocapsid structure.
2. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, described slaine A is AlCl
36H
2o, Zr (NO
3)
45H
2o, Ce (NO
3)
3, Fe
2(SO
4)
3in the combination of one or more; Described metal oxide is Al
2o
3, ZrO
2, CeO
2, Fe
2o
3the combination of one or more.
3. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 2, it is characterized in that, described slaine A is by AlCl
36H
2o and Zr (NO
3)
45H
2during O combination, its mol ratio by Al and Zr is 1:4 mixing composition; Described slaine A is by Ce (NO
3)
3with Zr (NO
3)
45H
2during O combination, its mol ratio by Ce and Zr is 1:3 mixing composition; Described slaine A is by Fe
2(SO
4)
3with Zr (NO
3)
45H
2during O combination, its mol ratio by Fe and Zr is 1:2 mixing composition.
4. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, is characterized in that, described alkaline solution is the one in sodium hydroxide solution and/or urea liquid; The concentration of described alkaline solution is 5-10mol/L.
5. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, described pectin is the low-ester pectin of esterification degree within the scope of 30%-40%.
6. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, described dispersant B is the one in carrene, dichloroethanes, chloroform.
7. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, described slaine B solution is the one in lanthanum chloride, calcium chloride, aluminium chloride and zirconium nitrate solution.
8. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, the average diameter of the micro-sphere absorption material of described nucleocapsid structure is 0.8-1.5mm, and wherein stratum nucleare thickness is 0.2-0.6mm, and shell thickness is 0.6-0.9mm.
9. the preparation method of pectin nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, in described step 4, calcium chloride solution can be substituted by the mixed solution of calcium chloride and strontium chloride, and calcium chloride and strontium chloride mix by weight 1:1 ~ 3.
10. the preparation method of pectin/metal oxide nucleocapsid structure micro-sphere absorption material as claimed in claim 1, it is characterized in that, after adding dispersant A in described step one, continue can to add ultrasonic wave in the stirring process of 0.5 ~ 1.5 hour and disperse, described hyperacoustic frequency is 10 ~ 20KHz; In described step 3, the preparation of mixed solution can add ultrasonic wave and mixes, and described hyperacoustic frequency is 10 ~ 20KHz, and described ultrasonic time is 1 ~ 2 hour.
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