CN103657608B - The preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material and application thereof - Google Patents

The preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material and application thereof Download PDF

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CN103657608B
CN103657608B CN201310625849.3A CN201310625849A CN103657608B CN 103657608 B CN103657608 B CN 103657608B CN 201310625849 A CN201310625849 A CN 201310625849A CN 103657608 B CN103657608 B CN 103657608B
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yeast
preparation
polymine
bag silicon
grafting
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CN103657608A (en
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欧红香
卞维柏
潘建明
吴才玉
黄卫红
朱亚梅
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Jiangsu University
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Jiangsu University
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Abstract

The invention belongs to technical field of environment function material preparation, relate to the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material of adsorbing separation cerium ion, strontium ion.Technical scheme of the present invention is: first mix ultrasonic to activated yeast and magnetic nanoparticle, and mixture and triethylamine and 3-chloropropyl trimethoxy silane react in toluene system, preparation magnetic bag silicon yeast; Then, adding polymine is function monomer, in cl radical and the polyethylenimine solution generation substitution reaction of magnetic bag silicon yeast surface, completes the grafting of polymine at magnetic bag silicon yeast surface, prepares Biocomposite material.The method increase the productive rate of host material, prepared adsorbent overcomes the deficiency that biomaterial mechanical strength is low in the past, there is good magnetic response character, quick separating can be realized, there is higher adsorption capacity and adsorption dynamics adsorption kinetics performance simultaneously, the object of the rapidly and efficiently adsorbing separation to cerium ion, strontium ion can be realized.

Description

The preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material and application thereof
Technical field
The present invention relates to magnetic bag silicon yeast grafting polymine Biocomposite material, particularly relate to the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material of adsorbing separation cerium ion, strontium ion, belong to technical field of environment function material preparation.
Background technology
Biological material source is wide, cheap, and has unique natural appearance structure, and especially microbial cell, advantages of environment protection inexpensive with it becomes the biological template of the micro-nano functional material of preparation of great potential.Yeast, as the important industrial microorganism of a class, is widely used in the fermentation industry such as food, beverage, but the weakness such as low, the easy blocking of yeast thalline mechanical strength, not easily collecting separation limit it extensively utilizes.But utilize yeast thalline as host material, not only can use it to that source is wide, cheap and easy to get, functional group enriches, compatible high and the advantages such as stable binding can be formed with inorganic material with organic matter, also can change its weakness by modifying its surface simultaneously.And the functional group that yeast surface is abundant, also provide the possibility of finishing.
Fe 3o 4(tri-iron tetroxide) nano particle is due to stronger superparamagnetism, become a kind of widely used magnetic-sensitive material, but simple ferriferrous oxide nano-particle is in use easily reunited, acid resistance is poor, easy leakage field after repeatedly using, ferriferrous oxide nano-particle is carried on yeast cell surface by us in the recent period, and carry out the process of bag silicon on its surface, solve magnetic material magnetic and reveal and Fe 3o 4the problem that nano particle is reunited.3-r-chloropropyl trimethoxyl silane (CP) not only can be used as coupling agent as silicon source.CP under certain condition, can react with hydroxyl (-OH), utilizes this character and host material to carry out being polymerized and form surperficial bag silicon materials, and it is coated to realize magnetic nano-particle.Simultaneously using branched polymine (PEI) as a kind of high molecular weight water soluble polymer function monomer, utilize CP as coupling agent by the grafting of PEI function monomer on bag silicon magnetic yeast host material, preparation magnetic bag silicon yeast grafting polymine Biocomposite material, and for the absorption of cerium ion, strontium ion in solution, there is not been reported in this research.
Some radioactive metal ions, such as cerium (Ce), strontium (Sr), uranium (U), caesium (Cs) etc. are in the exploitation of rare earth, can enter soil, water body, destroy ecological balance and the health of the mankind along with waste liquid is discharged.The same with other heavy metal ion, these metal ions have non-biodegradable and by food chain enrichment in health, can cause the canceration of histoorgan.Therefore, in the exploitation of Rare Earth Mine, waste liquid needs to carry out pretreatment effectively before discharge, alleviates the destruction of waste liquid to environment.
Summary of the invention
The object of the invention is to by two step solution polymerization process, preparation magnetic bag silicon yeast grafting polymine Biocomposite material; And the Biocomposite material of preparation is applied to the adsorbing separation of cerium ion, strontium ion.
The technical solution used in the present invention is:
First mix ultrasonic to activated yeast and magnetic nanoparticle, mixture and triethylamine and 3-chloropropyl trimethoxy silane react in toluene system, preparation magnetic bag silicon yeast (MY@SiO 2-Cl).Then, 3-chloropropyl trimethoxy silane is as coupling agent, and polymine (PEI) is function monomer, at MY@SiO 2the cl radical on-Cl surface and polyethylenimine solution generation substitution reaction, complete PEI at MY@SiO 2the grafting on-Cl surface, prepares Biocomposite material (MY@SiO 2-PEI), and for the cerium ion in adsorbing separation waste water and strontium ion.
(1) magnetic bag silicon yeast (MY@SiO 2-Cl) preparation: utilize solution polymerization process, by titanium dioxide
While silicon is coated on yeast cell surface, carry out coated to the nano ferriferrous oxide granule of cell surface, preparation process comprises:
A. be dissolved in NaCl solution by dry ferment, after uniform stirring, activation 50-70 min, obtain saccharomycete suspension;
B. thick bottom collected by centrifugation centrifuge tube yeast juice, adds Fe 3o 4nano particle, ultrasonic 1-10 minutes, wherein Fe 3o 4the particle diameter of nano particle is 800 nm;
C. yeast step B prepared and Fe 3o 4the mixture of nano particle proceeds in there-necked flask, adds toluene while stirring; In mixed solution, pass into nitrogen simultaneously, continue stirring 10-20 minutes;
D. in the mixture of step C preparation, triethylamine and 3-chloropropyl trimethoxy silane is added; Subsequently at 80-90 DEG C, reaction 9-11 hour;
E. collect separated product with permanent magnet, and with acetone, methyl alcohol and deionized water are washed successively, then dry at 40 DEG C, for subsequent use.
(2) solution polymerization process surface graft prepares Biocomposite material, and concrete steps are as follows:
A. get magnetic bag silicon yeast in beaker, then add polyethylenimine solution while stirring;
B. continue to stir, react 6-8 hour, make PEI function monomer fully graft on magnetic bag silicon yeast under 90-100 DEG C of condition, reaction generates highly cross-linked Biocomposite material;
C. product is collected with permanent magnet and is separated, and spend deionized water repeatedly, end-product is dried at 40 DEG C, for subsequent use.
Wherein the dry ferment described in steps A of step (1) and the ratio of NaCl solution are 0.5g:50-70mL, and wherein the mass concentration of NaCl solution is 0.8%-1%;
The Fe added described in step B 3o 4the amount of nano particle adds the Fe of 0.05-0.15g by every 0.5g dry ferment 3o 4nano particle;
The ratio adding toluene and dry ferment described in step C is 80-120mL:0.5g;
The ratio of the 3-chloropropyl trimethoxy silane described in step D and dry ferment is 2-4mL:0.5g, and the volume ratio of the triethylamine wherein added and 3-chloropropyl trimethoxy silane is 0.8-1.2:2-4.
Wherein the polyethylenimine solution described in steps A of step (2) and the ratio of magnetic bag silicon yeast are 60mL:0.2-0.4g, and wherein polyethylenimine solution concentration is 0.005-0.02 g/mL.
Prepare magnetic bag silicon yeast grafting polymine Biocomposite material according to the method described above, be applied to the trivalent cerium ion in adsorbing separation waste water and divalent strontium ions.
It is pure that agents useful for same of the present invention is analysis, and wherein dry ferment is purchased from Hubei Angel Yeast Co., Ltd.
Technological merit of the present invention:
Yeast thalline has the advantages such as wide, the with low cost and easy finishing of material source as host material; It is single step reaction that yeast bag silicon connects chlorine, improves the productive rate of intermediary substrate material, and surperficial bag silicon overcomes the deficiency that biomaterial mechanical strength is low in the past; Prepared material has magnetic response character, can realize quick separating, and magnetic nanoparticle is at silica interior simultaneously, and magnetic stability can be all better with heat endurance; After grafting function monomer polymine, enhance material to adsorption of metal ions performance, make material have higher adsorption capacity and adsorption dynamics adsorption kinetics performance, can realize the object of the rapidly and efficiently adsorbing separation to cerium ion, strontium ion, material has a good application prospect.
Accompanying drawing explanation
Fig. 1 is that two-step method prepares MY@SiO 2-Cl, MY@SiO 2the Technology Roadmap of-PEI adsorbent.
Fig. 2 is yeast in embodiment 1, MY@SiO 2-Cl, MY@SiO 2the infrared spectrogram of-PEI adsorbent.
Fig. 3 is the scanning electron microscope (SEM) photograph of yeast in embodiment 1, MY@SiO2-Cl, MY@SiO2-PEI adsorbent.
Fig. 4 is MY@SiO in embodiment 1 2-Cl, MY@SiO 2isopotential point (the pH of-PEI adsorbent zPC).
Fig. 5 is MY@SiO in embodiment 1 2-Cl, MY@SiO 2the contact angle of-PEI adsorbent.
Fig. 6 is Fe in embodiment 1 3o 4, MY@SiO 2-Cl and MY@SiO 2the hysteresis curve of-PEI and Magneto separate design sketch.
Detailed description of the invention
Absorption property evaluation experimental:
Carry out according to Staticadsorption experiment: by certain density cerium ion (Ce 3+), strontium ion (Sr 2+) be placed in the colorimetric cylinder of 25mL, place after adsorbing a period of time in water bath with thermostatic control, investigate effects of ion initial concentration, pH value, reaction time to adsorbent Ce 3+, Sr 2+impact.After absorption, use permanent magnet separating adsorbent, get supernatant inductance coupled plasma optical emission spectrophotometer Ce 3+, Sr 2+residual concentration, and according to result calculate adsorption capacity ( q e, mg g -1).
Q e,=[(C 0-C e)V]/W
Wherein, c 0(mg L -1) and c e(mg L -1) be the concentration of effects of ion after initial soln and adsorption equilibrium respectively, wg () is adsorbent amount, v(mL) be test fluid volume.
Embodiment 1:
(1) MY@SiO 2the preparation of-Cl:
Take 0.5g yeast, at 35 DEG C, activation 60 minutes in 60 mL physiological saline (sodium chloride solution of 0.9%); The dense thick sterilised yeast suspension of collected by centrifugation and with 0.1g Fe 3o 4ultrasonic 5 minutes of nano particle mixing; Mixed liquor is poured in the there-necked flask of 250 milliliters, and under mechanical agitation, add 100 milliliters of toluene liquid; Mixed toluene solution passes into nitrogen, adds the 3-chloropropyl trimethoxy silane of 1 milliliter of triethylamine and 3 milliliters after 15 minutes; Subsequently at 85 DEG C, react 9 hours, collect separated product, and utilize acetone with permanent magnet, methyl alcohol and deionized water cyclic washing successively, product is dried at 40 DEG C.
(2) MY@SiO 2the preparation of-PEI:
Take 0.3g magnetic yeast bag silicon product, be placed in the there-necked flask of 100 milliliters; The polymine pipetting 0.6g is dissolved in 60 ml deionized water, after stirring and dissolving, polyethylenimine solution is gently poured in 100 milliliters of there-necked flasks, fully stirs under mechanical agitation, and reacts 7 hours under 95 DEG C of conditions; Product is collected with permanent magnet and is separated, and spends deionized water repeatedly, 40 DEG C of dryings.
Fig. 2 is yeast in embodiment 1, MY@SiO 2-Cl, MY@SiO 2the infrared spectrogram of-PEI adsorbent.In figure, 1032,805,472 cm -1place is three characteristic peaks of silica, hydroxyl 3305 cm simultaneously on yeast -1comparatively MY@SiO 2-Cl dies down, and is displaced to 3297 cm -1, show that the hydroxyl on 3-chloropropyl trimethoxy silane and yeast there occurs reaction, achieve yeast bag silicon.575 cm in figure -1corresponding is Fe-O characteristic peak, shows that prepared material has magnetic.Compared with MY@SiO2-Cl, MY@SiO2-PEI adsorbent is at 1370 cm -1locate out the characteristic peak of Xian – C-N group, show PEI successfully grafting arrived MY@SiO2-Cl surface.In addition, at MY@SiO 2in-Cl, 705 cm -1corresponding is Cl peak, MY@SiO 2in-PEI adsorbent, Cl peak position is displaced to 719 cm -1, this further illustrates polymine and chlorine there occurs substitution reaction, successfully MY@SiO has been arrived in grafting 2-Cl surface.
Fig. 3 is the scanning electron microscope (SEM) photograph of yeast in embodiment 1, MY@SiO2-Cl, MY@SiO2-PEI adsorbent.Result shows, MY@SiO2-Cl increases than yeast slightly with MY@SiO2-PEI absorbent particles size, and after finishing, particle surface shows coarse.Because MY SiO2-Cl material surface-CH2-CH2-CH2-Cl hydrophobic grouping accounts for leading position, therefore surperficial smoother, coated silicon layer is high-visible.Water-soluble polyethylene imines (PEI) function monomer due to surface graft, the particle surface of MY@SiO2-PEI is more coarse, have bonding phenomenon between partial particulate.The above results also confirms that yeast and 3-chloropropyl trimethoxy silane (CP) are successfully made reaction, achieves yeast bag silicon, achieves the grafting of polymine (PEI) function monomer.
Fig. 4 is MY@SiO in embodiment 1 2-Cl, MY@SiO 2isopotential point (the pH of-PEI adsorbent zPC).Test result surface: MY SiO 2the pH of-Cl zPCbe 6.62, MY@SiO 2the pH of-PEI zPCbe 7.18.After grafting polymine, make MY@SiO 2-PEI surface has a large amount of basic group amido (-NH 2,-NH-), cause MY@SiO 2the pH of-PEI zPCraise, contribute to metal ion positively charged in adsorbing separation solution, thus improve the adsorption capacity of material.
Fig. 5 is MY@SiO in embodiment 1 2-Cl, MY@SiO 2the contact angle of-PEI adsorbent.MY@SiO as seen from the figure 2the contact angle of-Cl is 121 ° (> 90 °), in hydrophobicity, because this material surface has a large amount of hydrophobicity-CH 2-CH 2-CH 2-Cl group.After grafting water-soluble polyethylene imines, MY@SiO 2the contact angle of-PEI is 80 ° (< 90 °), becomes hydrophily, because of this material surface mainly hydrophilic group, presents hydrophilic nmature, be conducive to the absorption of adsorbent to effects of ion.MY@SiO 2the change of-PEI contact angle confirms further: polymine successfully grafting has arrived MY@SiO 2-Cl surface.
Fig. 6 is Fe in embodiment 1 3o 4, MY@SiO 2-Cl and MY@SiO 2the hysteresis curve of-PEI and Magneto separate design sketch.Result shows, Fe 3o 4magnetic saturation intensity be 74.88 emu/g, MY@SiO 2the magnetic saturation intensity of-Cl is 17.7 emu/g, MY@SiO 2-PEI magnetic saturation intensity is 10.03 emu/g.Because yeast and magnetic nanoparticle are by Silica-coated, so MY@SiO 217.7 emu/g are reduced to by force in the magnetic saturation of-Cl, and the grafting of polyethyleneimine polymer function monomer reduce further MY@SiO 2the magnetic saturation intensity of-PEI, from the photo figure, MY@SiO 2-PEI adsorbent can rapid aggregation under the effect of magnet, shows the requirement that the quick separating that this intensity can meet adsorbent is collected.
Embodiment 2:
(1) MY@SiO 2the preparation of-Cl:
Take 0.5g yeast, at 35 DEG C, activation 50 minutes in 50 mL physiological saline (sodium chloride solution of 0.8%); The about dense thick sterilised yeast suspension of collected by centrifugation and with 0.05g Fe 3o 4ultrasonic 1 minute of nano particle mixing; Mixed liquor is poured in 250 mL there-necked flasks, and under mechanical agitation, add 80 milliliters of toluene liquid; Mixed toluene solution passes into nitrogen, adds the 3-chloropropyl trimethoxy silane of 0.8 milliliter of triethylamine and 2 milliliters after 10 minutes; Subsequently at 80 DEG C, react 10 hours, collect separated product, and utilize acetone with permanent magnet, methyl alcohol and deionized water cyclic washing successively, product is dried at 40 DEG C.
(2) MY@SiO 2the preparation of-PEI:
Take 0.2 g magnetic yeast bag silicon product, be placed in the there-necked flask of 100 milliliters; The polymine pipetting 0.3g is dissolved in 60 ml deionized water, after stirring and dissolving, polyethylenimine solution is gently poured in 100 milliliters of there-necked flasks, fully stirs under mechanical agitation, and reacts 6 hours under 90 DEG C of conditions; Product is collected with permanent magnet and is separated, and spends deionized water repeatedly, 40 DEG C of dryings.
Embodiment 3:
(1) MY@SiO 2the preparation of-Cl:
Take 0.5g yeast, at 35 DEG C, activation 70 minutes in 70 mL physiological saline (sodium chloride solution of 1 %); The about dense thick sterilised yeast suspension of collected by centrifugation and with 0.15 g Fe 3o 4ultrasonic 10 minutes of nano particle mixing; Mixed liquor is poured in 250 mL there-necked flasks, and under mechanical agitation, add 120 milliliters of toluene liquid; Mixed toluene solution passes into nitrogen, adds the 3-chloropropyl trimethoxy silane of 1.2 milliliters of triethylamines and 4 milliliters after 20 minutes; Subsequently at 90 DEG C, react 11 hours, collect separated product, and utilize acetone with permanent magnet, methyl alcohol and deionized water cyclic washing successively, product is dried at 40 DEG C.
(2) MY@SiO 2the preparation of-PEI:
Take 0.4 g magnetic yeast bag silicon product, be placed in the there-necked flask of 100 milliliters; The polymine pipetting 1.2 g is dissolved in 60 ml deionized water, after stirring and dissolving, polyethylenimine solution is gently poured in 100 milliliters of there-necked flasks, fully stirs under mechanical agitation, and reacts 8 hours under 100 DEG C of conditions; Product is collected with permanent magnet and is separated, and spends deionized water repeatedly, 40 DEG C of dryings.
Embodiment 4:
MY@SiO2-Cl and MY@SiO2-PEI is to the Ce of variable concentrations 3+, Sr 2+ce in Ar ion mixing liquid 3+, Sr 2+the comparison of the absorption of ion:
Get the Ce that 25 ml initial concentrations are respectively 10,20,50,100,150,200,250,300,400 mg/L 3+/ Sr 2+mixed solution joins in colorimetric cylinder, regulates binary mixture solution ph to be 6.0, add 20 mg MY@SiO respectively with 0.1 mol/L watery hydrochloric acid and sodium hydroxide solution 2-Cl and MY@SiO 2-PEI adsorbent, test fluid is placed on after leaving standstill 12 h in the water-bath of 30 DEG C, supernatant liquor permanent magnet separated and collected, not by the Ce adsorbed 3+, Sr 2+ion concentration inductance coupled plasma optical emission spectrophotometer, and calculate adsorption capacity according to result.Result shows: MY@SiO 2-PEI is respectively 80.24 mg g to the maximal absorptive capacity of Ce3+ and Sr2+ in binary system -1with 63.51 mg g -1, MY@SiO 2the maximal absorptive capacity of-Cl is respectively 49.21 mg g -1with 34.51 mg g -1, MY@SiO 2the maximal absorptive capacity of-PEI is far away higher than the MY@SiO2-Cl of non-grafting PEI.
Embodiment 5:
In the different reaction time, MY@SiO2-Cl and MY@SiO2-PEI is to Ce 3+/ Sr 2+ce in mixed solution 3+, Sr 2+the comparison of ionic adsorption effect:
Get the Ce that 25ml two kinds of ion initial concentrations are 10mg/L 3+/ Sr 2+mixed solution adds in colorimetric cylinder, regulates binary mixture solution ph to be 6.0 add 20 mg MY@SiO respectively with 0.1 mol/L watery hydrochloric acid and sodium hydroxide solution 2-Cl and MY@SiO 2-PEI adsorbent, is placed on test fluid in the water-bath of 30 DEG C and leaves standstill after 3,5,8,10,20,40,60,120,180,360,720 minutes, and adsorbent is collected with permanent magnet and is separated, and supernatant liquor is not by the Ce adsorbed 3+, Sr 2+ion concentration inductance coupled plasma optical emission spectrophotometer, and calculate adsorption capacity according to result.Result shows: with the MY@SiO of non-grafting PEI 2-Cl compares, MY@SiO 2-PEI adsorbent have higher adsorption capacity ( q ce3+ =9.056 mg g -1, q sr2+ =4.637 mg g -1) and adsorption dynamics adsorption kinetics performance faster, time of equilibrium adsorption is shorter, based on chemisorbed.
Embodiment 6:
MY@SiO 2-Cl and MY@SiO 2-PEI is to the Ce of different pH value 3+/ Sr 2+ce in mixed solution 3+, Sr 2+the comparison of the adsorption effect of ion:
Get the Ce that 25ml two kinds of ion initial concentrations are 10 mg/L 3+/ Sr 2+mixed solution, regulates binary mixture solution ph 2-11 with 0.1 mol/L watery hydrochloric acid and sodium hydroxide solution, joins in colorimetric cylinder, add 20 mg MY@SiO respectively 2-Cl and MY@SiO 2-PEI adsorbent, is placed on test fluid in the water-bath of 30 DEG C and leaves standstill after 12 hours, and adsorbent is collected with permanent magnet and is separated, not by the Ce adsorbed 3+, Sr 2+ion concentration inductance coupled plasma optical emission spectrophotometer, calculates adsorption capacity at various ph values according to data result.Result shows: the initial pH of the suitableeest solution is 5.5-6, MY@SiO 2-PEI to two kinds of ions have higher adsorption capacity ( q ce3+ =8.81 mg g -1, q sr2+ =4.73 mg g -1).

Claims (4)

1. the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material, is characterized in that, carry out according to following steps:
(1) preparation of magnetic bag silicon yeast:
A. be dissolved in NaCl solution by dry ferment, after uniform stirring, activation 50-70 min, obtain saccharomycete suspension;
B. thick bottom collected by centrifugation centrifuge tube yeast juice, adds Fe 3o 4nano particle, ultrasonic 1-10 minutes, wherein Fe 3o 4the particle diameter of nano particle is 800 nm;
C. yeast step B prepared and Fe 3o 4the mixture of nano particle proceeds in there-necked flask, adds toluene while stirring; In mixed solution, pass into nitrogen simultaneously, continue stirring 10-20 minutes;
D. in the mixture of step C preparation, triethylamine and 3-chloropropyl trimethoxy silane is added; Subsequently at 80-90 DEG C, reaction 9-11 hour;
E. collect separated product with permanent magnet, and with acetone, methyl alcohol and deionized water are washed successively, then dry at 40 DEG C, for subsequent use;
(2) solution polymerization process surface graft prepares Biocomposite material, and concrete steps are as follows:
A. get magnetic bag silicon yeast in beaker, then add polyethylenimine solution while stirring;
B. continue to stir, react 6-8 hour, make PEI function monomer fully graft on magnetic bag silicon yeast under 90-100 DEG C of condition, reaction generates highly cross-linked Biocomposite material;
C. product is collected with permanent magnet and is separated, and spend deionized water repeatedly, end-product is dried at 40 DEG C, for subsequent use;
The Fe added described in the step B of wherein step (1) 3o 4the amount of nano particle adds the Fe of 0.05-0.15g by every 0.5g dry ferment 3o 4nano particle;
The 3-chloropropyl trimethoxy silane described in step D of step (1) and the ratio of dry ferment are 2-4mL:0.5g.
2. the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material according to claim 1, it is characterized in that, the dry ferment described in steps A of step (1) and the ratio of NaCl solution are 0.5g:50-70mL, and wherein the mass concentration of NaCl solution is 0.8%-1%; The ratio adding toluene and dry ferment described in step C is 80-120mL:0.5g; The volume ratio of the triethylamine added described in step D and 3-chloropropyl trimethoxy silane is 0.8-1.2:2-4.
3. the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material according to claim 1, it is characterized in that, the polyethylenimine solution described in steps A of step (2) and the ratio of magnetic bag silicon yeast are 60mL:0.2-0.4g, and wherein polyethylenimine solution concentration is 0.005-0.02 g/mL.
4. the preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material according to claim 1, it is characterized in that, the magnetic bag silicon yeast grafting polymine Biocomposite material of preparation is for the trivalent cerium ion in adsorbing separation waste water and divalent strontium ions.
CN201310625849.3A 2013-12-02 2013-12-02 The preparation method of magnetic bag silicon yeast grafting polymine Biocomposite material and application thereof Expired - Fee Related CN103657608B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5045201A (en) * 1988-09-21 1991-09-03 Glaverbel Glass microbeads for biochemical separation of material from a fluid medium
CN103055823A (en) * 2012-12-14 2013-04-24 江苏大学 Preparation method of surface print adsorbent of yeast template hollow silica-based material for adsorbing and separating strontium ions and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5045201A (en) * 1988-09-21 1991-09-03 Glaverbel Glass microbeads for biochemical separation of material from a fluid medium
CN103055823A (en) * 2012-12-14 2013-04-24 江苏大学 Preparation method of surface print adsorbent of yeast template hollow silica-based material for adsorbing and separating strontium ions and application thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Adsorption of phenol on a novel adsorption material PEI/SiO2;Fuqiang An et al.;《Journal of Hazardous Materials》;20070803;第152卷;第1186-1191页 *
Chelating adsorption properties of PEI/SiO2 for plumbum ion;Fuqiang An et al.;《Journal of Hazardous Materials》;20061130;第145卷;第495-500页 *
Polyethyleneimine gel-coat on silica.High uranium capacity and fast kinetics of gel-coated resin;M.Chanda et al.;《Reactive Polymers》;19951231;第25卷;第25-36页 *
Uptake of heavy metals from synthetic aqueous solutions using modified PEI-silica gels;M.Ghoul et al.;《Water Research》;20031231;第37卷;第729-734页 *
改性硅基微/纳米材料及其在分离化学中的应用研究进展;刘燕等;《冶金分析》;20101231;第30卷(第9期);第37-46页 *
黄卫红等.酵母/硅复合材料对铈(III)的吸附性能及机理.《江苏大学学报(自然科学版)》.2013,第34卷(第2期),第212-216页. *

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