CN103862037B - The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way - Google Patents

The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way Download PDF

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CN103862037B
CN103862037B CN201410069833.3A CN201410069833A CN103862037B CN 103862037 B CN103862037 B CN 103862037B CN 201410069833 A CN201410069833 A CN 201410069833A CN 103862037 B CN103862037 B CN 103862037B
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iron
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CN103862037A (en
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吕晓书
胡运俊
薛晓芹
朱瑾
徐新华
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Zhejiang University ZJU
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Abstract

The invention belongs to biomaterial embedding techniques field, method embeds preparation and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system in particular to a kind of polyvinyl alcohol-sodium alginate biomaterial.The iron content bead that the present invention prepares, is applicable to conventional Zero-valent Iron pollution amelioration field, reduces potential risks in Application of micron simultaneously, reaches the object of safe and efficient process.The preparation method of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and a pre-treatment way, obtain the stabilizing agent of ferriferrous oxide particles as nano zero valence iron particle using coprecipitation, preparation Zero-valent Iron-tri-iron tetroxide double nano material; Then select suitable biomaterial to carry out embedding treatment to above-mentioned double nano material, obtain embedding bead; Finally acid treatment and reduction treatment are carried out to embedding bead, obtain the biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead of stability and high efficiency.

Description

The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way
Technical field
The invention belongs to biomaterial embedding techniques field, method embeds preparation and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system in particular to a kind of polyvinyl alcohol-sodium alginate biomaterial.The iron content bead that the present invention prepares, is applicable to conventional Zero-valent Iron pollution amelioration field, reduces potential risks in Application of micron simultaneously, reaches the object of safe and efficient process.
Background technology
Extraction and nanometer iron metal (Fe 0) electrode potential is low, specific area is large, can, fast by the reduction of ion stronger for oxidisability, compound and partial organic substances, be desirable environment in-situ immobilization medium.But particle is little, surface is active, and easy and surrounding medium (water, air etc.) reacts, and forms metal hydroxides or carbonate passivation layer, hinder Fe at particle surface 0with the haptoreaction of pollutant.Meanwhile, due to magnetic force between self gravitation, particle etc., nanometer Fe 0particle there will be agglomeration, greatly reduces surface-active site, and loses animal migration and transitivity, finally reduces nanometer Fe 0effective rate of utilization.Ferriferous oxide is (as Fe 3o 4) itself is very little to the removal effect of pollutant, but as it and nanoscale Fe 0in conjunction with after, not only can be gathered in zero-valent iron particle surrounding and provide support for it, prevent nanometer Fe 0polymerization, and due to Fe 2+with Fe 3+be lack of alignment in tri-iron tetroxide octahedral structure, electronics can shift rapidly between two of iron kind of oxidation state, thus can provide new electron channel for Zero-valent Iron, improves Fe 0electron transmission ability.Therefore, Zero-valent Iron-tri-iron tetroxide double nano system is used to be used for environmental pollution reparation, compared to pure Fe 0system, can show good synergy, improves treatment effeciency.
Along with the development of nanometer recovery technique, nano material potential risks also obtain attention gradually.Nano particle is while application, and the environmental hazard that its diffusion mobility, conversion deposition etc. are brought, and the bio-toxicity etc. of nano-scale are all the problems of restriction nano material practical application.Consider that nano-grain is little, easily run off, the microbial of the feature such as to be affected by the external environment larger and biological prosthetic middle use is similar, immobilized microorganism technology can be entered into the stabilisation of nano particle.
Immobilized microorganism technique is the method for applied chemistry or physics, is positioned the space field limited by free microorganism, and makes it keep active, possesses the feature recycled.Microbial immobilized method is different according to the kind difference of fixed microorganism, mainly contains investment, cross-linking method, several large class of absorption method.Wherein, investment utilizes macromolecule carrier to be trapped in macromolecule network by free microorganism, but still substrate infiltration can be allowed to react with the various enzymes of thalline or emiocytosis.This method stable operation, less to the activity influence of microorganism, the immobilized microspheres intensity of making is high, and close structure, to being enough to prevent cell seepage, is study immobilization technology method the most widely at present.Conventional bio-carrier mainly contains agar, sodium alginate (CA), polyvinyl alcohol (PVA), polyacrylamide (PAM) etc., microorganism can be embedded in gel inside thus reach the object of fixed cell by them when forming gel, obtain more research application in the treatment of waste water.
The research that immobilization technology embedding iron material is applied to environmental pollution reparation receives publicity gradually, the people such as Banerjee (A.Banerjee, D.Nayak, S.Lahiri.Applied Radiation and Isotopes, 2007,65:769-775) use sodium alginate mixing Fe 3+ion, drips in calcium chloride solution, forms calcium alginate embedded Fe bead, for the Adsorption of As (VI), under pH is 3.0 conditions, can obtain optimal adsorption effect; The people such as Rocher (V.Rocher, et al.Water research, 2008,42:1290-1298) sodium alginate, magnetic iron ore, active carbon are formed solution, strong agitation makes its Homogeneous phase mixing, dropwise join in calcium chloride solution and form embedding bead, this bead has good adsorption selection effect to methyl blue dye; The people such as Bezbaruah (A.N.Bezbaruah, et al.Journal of Hazardous Materials, 2009,166:1339-1343) nano zero valence iron prepared in advance is directly mixed with sodium alginate gel, in calcium chloride solution, solidify more than at least 6 hours, obtained bead has good removal effect to nitrate; The people such as Kim (H.Kim, et al.Journalof Hazardous Materials, 2010,176:1038-1043) also prepare the removal of sodium alginate to embed nano zero valence iron bead for trichloro-ethylene, but first by Fe 3+after ion forms bead with sodium alginate mixing titration, re-use sodium borohydride and the iron ion in bead is reduced to Fe 0.
Embedding iron material bead prepared by said method, although show good stabilization effect to nano material, ubiquity intensity is low, structure easily broken, shortcoming that recycling rate of waterused is low, inner Fe simultaneously 0by oxidation to a certain extent in preparation process, affect its result of use, make the overall removal efficiency of embedding bead to pollutant on the low side.
Summary of the invention
Bioencapsulation technology is used for the stabilisation of nano-iron material by the present invention, and object is to provide one can ensure nano material service efficiency, can reduce again the way of its environmental risk.Invention relates to the bimetallic technology of preparing of Zero-valent Iron-ferriferrous oxide nano, and biomaterial embedded nano bimetallic forms the way of immobilized spherule, improves the pretreatment technology of embedding bead physical and chemical performance, and the purposes of system in environment remediation.
The preparation method of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and a pre-treatment way, obtain the stabilizing agent of ferriferrous oxide particles as nano zero valence iron particle using coprecipitation, preparation Zero-valent Iron-tri-iron tetroxide double nano material; Then select suitable biomaterial to carry out embedding treatment to above-mentioned double nano material, obtain embedding bead; Finally acid treatment and reduction treatment are carried out to embedding bead, obtain the biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead of stability and high efficiency.
Concrete operation step is as follows:
(1) Zero-valent Iron-tri-iron tetroxide double nano material is prepared: first, under nitrogen protection, Fe (III) and Fe (II) molysite of certain molal weight ratio is added in there-necked flask, add thermal agitation, be fully dissolved in after in deionized water, dropwise drip alkaline solution, regulation system pH is to alkalescence, aging 2 ~ 4 hours of constant temperature, obtained nano ferriferrous oxide granule, separating, washing is placed on another there-necked flask; Then, add Fe (II) solution, constant temperature stirs, and dropwise drips excess reducing solution, reacts after 1 hour, magnetic separation, spends deionized water to neutral, obtains Zero-valent Iron-tri-iron tetroxide double nano material.
(2) preparation embedding bead: first, bioencapsulation heating materials is dissolved in 50mL deionized water, is uniformly mixed to form gel, be cooled to room temperature, add step (1) and prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and leave standstill 30min; Then, draw above-mentioned iron content biogel with syringe, be added drop-wise in crosslinking agent, vibration is also preserved after 12 ~ 24 hours in crosslinking agent, transfers to and adds in solid-liquid, reinforce; Finally, spend deionized water, obtained embedding bead.
(3) embed bead pre-treatment step: first, gained embedding bead prepared by step (2) and be placed in acid solution, 30 DEG C, 120 revs/min constant temperature water bath vibrations were taken out after 5 ~ 45 minutes, washed with de-ionized water; Then, be added in reducing solution by acidifying bead, 30 DEG C, 120 revs/min constant temperature water bath vibrations were taken out after 15 ~ 45 minutes, with deionized water rinsing, and obtained stability and high efficiency biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead.
Further, step (1) described Fe (III) salt is FeCl 36H 2o or Fe 2(SO 4) 3xH 2one in O, Fe (II) salt is FeCl 24H 2o or FeSO 47H 2one in O.
Further, step (1) described Fe (III) and Fe (II) salt molar concentration rate Fe 3+: Fe 2+=2.0 ~ 1.6:1.0.
Further, the alkaline solution described in step (1) is the one of ammoniacal liquor or NaOH solution.
Further, the reducing solution described in step (1) is NaBH 4the aqueous solution.
Further, the described bioencapsulation material of step (2) is at least one in polyvinyl alcohol, sodium alginate, calcium alginate, agar, polyacrylamide.
Further, the described bioencapsulation material of step (2) is polyvinyl alcohol and sodium alginate, and the mass ratio of polyvinyl alcohol and sodium alginate is 5:1.5.
Further, step (2) the described crosslinking agent at least one that to be solution be in boric acid, calcium chloride solution.
Further, step (2) described crosslinking agent is boric acid-anhydrous chlorides of rase calcium solution, and the mass ratio of boric acid and anhydrous calcium chloride is 2 ~ 8:0.5 ~ 1.5.
Further, the NaSO that solid-liquid is mass concentration 3 ~ 10wt% is added described in step (2) 4solution.
Further, step (3) described acid solution is finite concentration HCl or HNO 3the one of solution.
Further, the reducing solution described in step (3) is certain density NaBH 4the aqueous solution.
Advantage of the present invention and beneficial effect:
1) biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano particle is used, can while reservation nano material efficient disposal ability, lower the bio-toxicity of nano-scale, and subtract less granular loss greatly, thus reduce migration when nano material uses, the environmental risk brought of conversion process;
2) embedding system has the features such as iron dissolution rate is low, and water outlet is limpid, and water quality is good.Meanwhile, lock out operation is simple, only uses simple grid device in actual applications, just can reach the effect be separated completely, be conducive to the recycling of system.In addition, embedding system can be applicable to aerobic environment, compared to the pure nano zero valence iron particle that passivation occurs rapidly at aerobic environment, expands the scope of application;
3) the pre-treatment way of embedding iron material bead is proposed in the present invention, wherein acidification step strengthens the physical property of immobilized spherule greatly, through the bead of acidification, while volume reduces slightly, mechanical strength, elasticity etc. are increased, in long-term concussion process can holding structure complete.After reduction step is used in acidification step, partially oxidized zero-valent iron particle in embedding in early stage and acidification can be ensured again to revert to zero-valent state, strengthen the chemical treatment efficiency of bead.
Accompanying drawing explanation
Fig. 1 is according to the embodiment of the present invention, the transmission electron microscope picture of the Zero-valent Iron obtained-tri-iron tetroxide double nano material;
Fig. 2 is according to the embodiment of the present invention, the contrast photo not embedding and embed the biomaterial bead of iron double nano material obtained;
Fig. 3 is according to the embodiment of the present invention, and the biomaterial of preparation embedding Zero-valent Iron-tri-iron tetroxide double nano bead is in pretreatment process (under a moisture state; After b natural drying) change comparison diagram, the bead of natural drying after acidification in b is yellow;
Fig. 4 is according to the embodiment of the present invention, the embedding bead of preparation and pure Zero-valent Iron-tri-iron tetroxide system after Cr (VI) Transformatin completes, the separation case of system and effluent quality comparison diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, content of the present invention is described further, make object of the present invention and effect more obvious, but protection scope of the present invention is not limited to these embodiments.
In the following example, method therefor if no special instructions, is conventional method.Material required in the following example or reagent, be market if no special instructions and buy.
Embodiment 1:
Use way of the present invention to prepare polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide embedding bead, and applied in the reparation of Cr (VI) polluted-water, it uses step as follows:
(1) 0.745g FeCl is taken 36H 2o and 0.3825g FeSO 47H 2o, is placed in 250mL there-necked flask, adds 100mL deionized water, and 60 DEG C of waters bath with thermostatic control are stirred.Under flow velocity 150mL/min nitrogen protection, dropwise drip the ammoniacal liquor of 8mol/L, making reaction system be alkalescence is more than 11 to pH; aging 2 hours of constant temperature; obtained nano ferriferrous oxide granule, transfers to after separating, washing in 1L there-necked flask, adds containing 0.375gFeSO 47H 2the 400mL deionized water solution of O, constant temperature stirs, and dropwise drips containing 0.35g NaBH 4100mL deionized water solution, react after 1 hour, Magneto separate, spend deionized water to neutral, obtain Zero-valent Iron-tri-iron tetroxide double nano material.
(2) 5.0g polyvinyl alcohol is taken and 1.5g sodium alginate is dissolved in 50mL deionized water respectively, 60 DEG C of heating, after dissolving completely, both are uniformly mixed to form gel, be cooled to room temperature, add step (1) and prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and leave standstill 30min; Then, preparation contains the aqueous solution of concentration 5wt% boric acid and 1.5wt% anhydrous calcium chloride as crosslinking agent, draws above-mentioned iron content biogel, be added drop-wise in crosslinking agent with syringe, and vibration is also preserved after 12 hours in crosslinking agent, transfers to the NaSO of 6wt% 4solution is reinforced.Finally, spend deionized water, obtained embedding bead.
(3) the embedding bead being prepared by step (2) gained is placed in 1.0mol/L hydrochloric acid solution, takes out, washed with de-ionized water after 30 DEG C, 120 revs/min constant temperature water baths vibrate 15 minutes; Then, acidifying bead is added to 0.05mol/L NaBH 4carry out reduction treatment in solution, take out after 30 DEG C, 120 revs/min constant temperature water baths vibrate 30 minutes, with deionized water rinsing, obtained stability and high efficiency biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead.
Fig. 1 is that in double nano material, zero-valent iron particle size is at 100 ran according to above the step Zero-valent Iron-tri-iron tetroxide double nano material prepared and the projection electron microscopic picture embedding bead, and around namely the particle of less 10-30 ran is tri-iron tetroxide.Fig. 2 is pure polyvinyl alcohol-sodium alginate bead and the bead after having embedded above-mentioned Zero-valent Iron-ferriferrous oxide material, and bead becomes ater from pure white, illustrates that iron material is embedded in biomaterial by uniform mixing.
Take polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide bead that 8.0g is prepared by above step, join in Cr (VI) aqueous solution that 100mL concentration is 5-40mg/L, the initial pH of solution is regulated to be 3.0-11.0,30 DEG C, rotating speed 150 revs/min of constant temperature water bath vibrations, react.Sample at regular intervals,
By measuring Cr (VI) content after 0.45 μm of membrane filtration, and calculate clearance, computing formula is as follows:
η % = C 0 - C t C 0
Wherein: η % is the clearance of t system to Cr (VI); C 0for the initial concentration of Cr (VI), mg/L; C tfor Cr (VI) is in the concentration of t, mg/L.
Table 1 is that to tie up to initial pH be under 5.0 conditions to this spherula, to the removal efficiency of 5-30mg/L Cr (VI) in system.Can see, in 24 little the reaction times, Cr (VI) all can remove completely, but reaches the time of removing completely and be increased to 18 hours from 1 hour, and to clearance in 24 hours of the Cr (VI) of 40mg/L about 89.3%.
The removal effect of bead is embedded under different initial Cr (VI) concentration of table 1
Initial Cr (VI) concentration (mg/L) 5 10 20 30 40
12 hours clearances 100% 100% 97.7% 93.1% 79.5%
Remove required time (h) completely 0.5 4 18 24 --
Table 2 is that to tie up to initial concentration be in 10mg/L Cr (VI) solution to this spherula, the removal effect under different pH condition.Obviously, remove best results under acid condition, along with the rising of pH, removal efficiency reduces gradually.When pH rises to 11.0, in 12 hours, the clearance of system is only 76.3%.
The removal effect of bead is embedded under the different initial pH value of table 2
Initial pH value 3.0 5.0 7.0 9.0 11.0
12 hours clearances 100% 97.7% 88.3% 80.9% 76.3%
Embodiment 2:
When research the application of the invention is prepared polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide double nano system bead, different preparations and pre-treating method are on the impact of obtained bead removal ability, and concrete steps are as follows:
Embodiment 2-10 adopts different proportion polyvinyl alcohol (PVA) and sodium alginate (SA) preparation embedding Zero-valent Iron-tri-iron tetroxide double nano material bead, and for the treatment of Cr (VI).Other operating procedures are with embodiment 1, and the removal efficiency of material rate and correspondence is as shown in table 3:
The removal effect of the different polyvinyl alcohol of table 3 and sodium alginate ratio embedding bead
Embodiment 2 3 4 5 6 7 8 9 10
SA:PVA(wt%) 0.5:2 1.5:2 2.5:2 0.5:5 1.5:5 2.5:5 0.5:8 1.5:8 2.5:8
12 hours clearances 60.2% 90.3% 86.3% 66.2% 97.7% 97.9% 87.3% 84.6% 87.3%
Although the clearance of ratio 2.5:5 is slightly better than 1.5:5, under 2.5:5, the difficulty preparing bead is large, because viscosity is high, drip ball difficulty, bead easily trails, because optimal proportion is still advisable with 1.5:5.
Embodiment 11-17 adopts different pre-treatments step (different acidifying and recovery time) to process embedding bead, and uses it for process Cr(VI).Other operating procedures are with embodiment 1, and the removal efficiency of Pretreatment and correspondence is as shown in table 4:
The removal effect of bead under table 4 different pre-treatments condition
Embodiment 18:
When research the application of the invention is prepared polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide double nano system bead, pre-treatment step is on the impact of bead performance, in bead use procedure iron diafiltration situation and recycling situation, concrete steps are as follows:
1) by according to the bead without pre-treatment bead, only acidification bead, acidifying+reduction bead three kinds of states prepared in embodiment 1 step, the water bath with thermostatic control vibration case being placed in 30 DEG C, 150 revs/min is respectively cultivated, percentage of damage in research process, to characterize its mechanical strength.Simultaneously by air-dry under field conditions (factors) for another group bead, the situation of change of bead in research process;
2) 8.0g is joined 100mL containing in Cr (VI) aqueous solution of 20mg/L through the polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide bead of pre-treatment, be 5.0 at initial pH, in the water bath with thermostatic control concussion case of 30 DEG C, 150 revs/min, study the change of concentration of iron in system in removal process;
3) under the condition that step (2) is identical, react after 24 hours, isolate bead, after rinsing well, re-start the pre-treatment step described in the present invention, regeneration process is carried out to bead.The bead regenerated, after washes clean, recycles, and measures the removal efficiency at every turn recycling middle Cr (VI).Meanwhile, use without the Zero-valent Iron-tri-iron tetroxide system embedded as a control group, carry out recycling test simultaneously.
Result shows, and embedding bead is after experience acidification, and mechanical performance improves greatly, without any Fragmentation Phenomena in the incubation of 15 days, and almost completely broken within one week without the embedding bead of pre-treatment.Fig. 3 (a) is the cosmetic variation figure using bead in pretreatment process of the present invention, and during acidified process, the volume of bead obviously reduces, and may be the reason that mechanical strength improves.Meanwhile, the bead (shown in Fig. 3 (b)) after natural air drying still can keep good form, and does not carry out the bead of pre-treatment, structural breakdown, and embedded material is separated out.If but without reduction treatment, little club becomes yellow, illustrate that inner iron is easily oxidized, and reduction treatment avoids this process, thus be conducive to the electronation performance improving bead.
Table 5 shows, and in use, in solution, iron content can control within 2-3mg/L embedding system under normal circumstances, and illustrate that iron diafiltration ratio from bead is lower, the migration of iron is inhibited.
Table 5 embeds bead removes Fe in course of reaction infiltration capacity at Cr (VI)
Reaction time (min) 15 30 60 120 360 720 1080 1440
Total Fe content (mg/L) in solution 2.2 2.1 1.8 1.4 1.4 1.1 0.9 0.8
Fe (II) content (mg/L) in solution 0.2 0.2 0.5 0.3 0.6 0.2 0.3 0.2
Fe (III) content (mg/L) in solution 1.9 1.8 1.3 1.1 0.8 0.9 0.6 0.6
Table 6 is the contrasts reusing embedding system and independent Zero-valent Iron-tri-iron tetroxide double nano system in aerobic environment, result shows, embedding system still can keep the clearance of 69.8% in using at the 4th time, and pure system is when third time uses, clearance is just reduced within 50%, illustrates that the repeated practicality of Zero-valent Iron-tri-iron tetroxide obtains certain raising.In addition, Fig. 4 be preparation embedding bead and pure Zero-valent Iron-tri-iron tetroxide system after Cr (VI) Transformatin completes, the separation case of system and effluent quality comparison diagram.Embedding bead system is by salvaging or grid device and separable, and water outlet is limpid, no suspended substance, and needs externally-applied magnetic field to assist to be separated without the pure Zero-valent Iron-tri-iron tetroxide system of embedding, and the tiny iron particle of part is easily trapped in processed water body.
Pure Zero-valent Iron-the tri-iron tetroxide of table 6 and embedding bead reuse removal effect contrast to Cr (VI)
Cycle-index For the first time For the second time For the third time 4th time
Zero-valent Iron-tri-iron tetroxide 96.3% 68.6% 49.7% --
Embedding iron bead 100% 88.9% 84.2% 69.8%
Proved by embodiment, the biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system bead prepared by the present invention has good Cr (VI) removal ability.Preparation process is simple, mild condition, easy controlled operation, the system convenient separation simultaneously prepared, and recycling rate of waterused is high, environmental friendliness, is a kind of nano zero valence iron improving technology preferably, has broad application prospects.

Claims (8)

1. the preparation method of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way, it is characterized in that: obtain the stabilizing agent of ferriferrous oxide particles as nano zero valence iron particle using coprecipitation, preparation Zero-valent Iron-tri-iron tetroxide double nano material; Then select suitable biomaterial to carry out embedding treatment to above-mentioned double nano material, obtain embedding bead; Finally acid treatment and reduction treatment are carried out to embedding bead, obtain biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead,
Specifically comprise the steps:
(1) Zero-valent Iron-tri-iron tetroxide double nano material is prepared: first, under nitrogen protection, Fe (III) and Fe (II) molysite is added in there-necked flask, add thermal agitation, be fully dissolved in after in deionized water, dropwise drip alkaline solution, regulation system pH is to alkalescence, aging 2 ~ 4 hours of constant temperature, obtained nano ferriferrous oxide granule, separating, washing is placed on another there-necked flask; Then, add Fe (II) solution, constant temperature stirs, and dropwise drips excess reducing solution, reacts after 1 hour, magnetic separation, spends deionized water to neutral, obtains Zero-valent Iron-tri-iron tetroxide double nano material;
(2) preparation embedding bead: first, bioencapsulation heating materials is dissolved in 50mL deionized water, is uniformly mixed to form gel, be cooled to room temperature, add step (1) and prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and leave standstill 30min; Then, draw above-mentioned iron content biogel with syringe, be added drop-wise in crosslinking agent, vibration is also preserved after 12 ~ 24 hours in crosslinking agent, transfers to and adds in solid-liquid, reinforce; Finally, spend deionized water, obtained embedding bead;
(3) embed bead pre-treatment step: first, gained embedding bead prepared by step (2) and be placed in acid solution, 30 DEG C of constant temperature water bath vibrations were taken out after 5 ~ 45 minutes, washed with de-ionized water; Then, be added in reducing solution by acidifying bead, 30 DEG C of constant temperature water bath vibrations were taken out after 15 ~ 45 minutes, with deionized water rinsing, and the biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead of obtained stability and high efficiency.
2. a kind of biomaterial according to claim 1 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: step (1) described Fe (III) salt is FeCl 36H 2o, Fe (II) salt is FeCl 24H 2o or FeSO 47H 2one in O, is dissolved in the molar concentration rate Fe in deionized water 3+: Fe 2+=2.0 ~ 1.6:1.
3. a kind of biomaterial according to claim 1 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: the alkaline solution described in step (1) is the one of ammoniacal liquor or NaOH solution, and described reducing solution is NaBH 4the aqueous solution.
4. a kind of biomaterial according to claim 1 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: the described bioencapsulation material of step (2) is at least one in polyvinyl alcohol, sodium alginate, calcium alginate, agar, polyacrylamide.
5. a kind of biomaterial according to claim 1 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: the described bioencapsulation material of step (2) is polyvinyl alcohol and sodium alginate, the mass ratio of polyvinyl alcohol and sodium alginate is 5:1.5.
6. a kind of biomaterial according to claim 1 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: the cross-linking agent solution described in step (2) is at least one in boric acid, calcium chloride solution.
7. a kind of biomaterial according to claim 6 embeds preparation method and the pre-treatment way of Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: the crosslinking agent described in step (2) is boric acid-anhydrous chlorides of rase calcium solution, the mass ratio of boric acid and anhydrous calcium chloride is 2 ~ 8:0.5 ~ 1.5.
8. according to preparation method and the pre-treatment way of the arbitrary described a kind of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system of claim 1-7, it is characterized in that: described in step (2), add the NaSO that solid-liquid is mass concentration 3 ~ 10wt% 4solution.
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