CN103862037A - Preparation method and preprocessing method of biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system - Google Patents
Preparation method and preprocessing method of biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system Download PDFInfo
- Publication number
- CN103862037A CN103862037A CN201410069833.3A CN201410069833A CN103862037A CN 103862037 A CN103862037 A CN 103862037A CN 201410069833 A CN201410069833 A CN 201410069833A CN 103862037 A CN103862037 A CN 103862037A
- Authority
- CN
- China
- Prior art keywords
- iron
- zero
- embedding
- biomaterial
- tri
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the technical field of biomaterial embedment and particularly relates to a preparation method and a preprocessing method of a polyvinyl alcohol-sodium alginate biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system. Ferrous pellets which are prepared by the method are applicable to the field of conventional zero-valent-iron pollution remediation, and meanwhile, potential risks in the application of nanometer materials are decreased, so that the purpose of safe and highly-efficient processing is achieved. The preparation method and the preprocessing method of the biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system comprise the following steps of preparing a zero-valent-iron-ferroferric-oxide double-nanometer material by using ferroferric-oxide granules which are prepared by a coprecipitation method as a stabilizing agent of nanometer zero-valent-iron granules; then carrying out embedded processing on the double-nanometer material by selecting a proper biomaterial to obtain embedded pellets; finally carrying out acid processing and reduction processing on the embedded pellets to obtain stable and highly-efficient biomaterial-embedded zero-valent-iron-ferroferric-oxide pellets.
Description
Technical field
The invention belongs to biomaterial embedding techniques field, method is particularly related to a kind of preparation and pre-treatment way of polyvinyl alcohol-sodium alginate biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system.The iron content bead that the present invention prepares, pollutes reparation field applicable to conventional Zero-valent Iron, reduces potential risks in Application of micron simultaneously, reaches the object of safe and efficient processing.
Background technology
Extraction and nanometer iron metal (Fe
0) electrode potential is low, specific area is large, can, fast by ion stronger oxidisability, compound and partial organic substances reduction, be that desirable environment original position is repaired 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 at particle surface, has hindered Fe
0haptoreaction with pollutant.Meanwhile, due to magnetic force between self gravitation, particle etc., nanometer Fe
0particle there will be agglomeration, has greatly reduced 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+in tri-iron tetroxide octahedral structure, be lack of alignment, electronics can shift rapidly between two of iron kind of oxidation state, thereby can provide new electron channel for Zero-valent Iron, improves Fe
0electronics transmission capacity.Therefore, use Zero-valent Iron-tri-iron tetroxide double nano system 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 have also obtained attention gradually.Nano particle, in application, its diffusion mobility, transforms the environmental hazards that bring such as deposition, and the bio-toxicity of nano-scale etc., be all the problem of restriction nano material practical application.Consider that nano-grain is little, easily run off, the microbial using in the feature such as be affected by the external environment larger and biological restoration is similar, microbial immobilized 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 of restriction by free microorganism, and makes it keep active, possesses the feature of recycling.Microbial immobilized method is different and different according to the kind of fixing microorganism, mainly contains investment, cross-linking method, several large classes of absorption method.Wherein, investment is to utilize macromolecule carrier that free microorganism is trapped in macromolecule network, but still can allow the various enzymes of substrate infiltration and thalline or emiocytosis to react.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 the immobilization technology method the most widely of studying at present.Conventional bio-carrier mainly contains agar, sodium alginate (CA), polyvinyl alcohol (PVA), polyacrylamide (PAM) etc., thereby they can be embedded in microorganism the inner object that reaches fixed cell of gel in the time forming gel, in wastewater treatment, obtain more research application.
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 and in calcium chloride solution, forms calcium alginate embedded Fe bead, for the Adsorption of As (VI), is under 3.0 conditions at pH, 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 to solution, strong agitation is evenly mixed it, dropwise join in calcium chloride solution and form embedding bead, this bead has good selection adsorption effect to methyl blue dyestuff; The people such as Bezbaruah (A.N.Bezbaruah, et al.Journal of Hazardous Materials, 2009,166:1339-1343) nano zero valence iron of preparation in advance is directly mixed with sodium alginate gel, in calcium chloride solution, solidify more than at least 6 hours, make bead nitrate is had to good removal effect; The people such as Kim (H.Kim, et al.Journal of 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+ion re-uses sodium borohydride the iron ion in bead is reduced to Fe after forming bead with sodium alginate mixing titration
0.
Embedding iron material bead prepared by said method, although nano material has been shown to good stabilization effect, ubiquity intensity is low, easily broken, shortcoming that recycling rate of waterused is low of structure, inner Fe simultaneously
0in preparation process, be subject to oxidation to a certain extent, affect its result of use, make embedding bead on the low side to the overall removal efficiency of pollutant.
Summary of the invention
The present invention is the stabilisation for nano-iron material by bioencapsulation technology, 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.
Preparation method and the pre-treatment way of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system, make 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 embedding bead is carried out to acid treatment and reduction processing, obtain biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead of stability and high efficiency.
Concrete operation step is as follows:
(1) prepare Zero-valent Iron-tri-iron tetroxide double nano material: first, under nitrogen protection, to the Fe (III) and Fe (II) molysite that add certain molal weight ratio in there-necked flask, add thermal agitation, after being fully dissolved in deionized water, dropwise drip alkaline solution, regulation system pH is to alkalescence, aging 2～4 hours of constant temperature, makes nano ferriferrous oxide granule, and separating, washing is placed on another there-necked flask; Then, add Fe (II) solution, constant temperature stirs, and dropwise drips excessive reducing solution, reacts after 1 hour, and magnetic separation, to neutral, obtains Zero-valent Iron-tri-iron tetroxide double nano material with deionized water washing.
(2) prepare embedding bead: first, bioencapsulation material heating for dissolving, in 50mL deionized water, is uniformly mixed to form to gel, is cooled to room temperature, add step (1) to prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and standing 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, reinforces; Finally, with deionized water washing, make embedding bead.
(3) embedding bead pre-treatment step: first, step (2) is prepared to gained embedding bead 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, acidifying bead is added in reducing solution, 30 DEG C, 120 revs/min constant temperature water bath vibrations were taken out after 15～45 minutes, with deionized water rinsing, made stability and high efficiency biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead.
Further, the described Fe of step (1) (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, the described Fe of step (1) (III) and Fe (II) salt molar concentration rate Fe
3+: Fe
2+=2.0～1.6:1.0.
Further, the described alkaline solution of step (1) is the one of ammoniacal liquor or NaOH solution.
Further, the described reducing solution of 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, the described crosslinking agent of step (2) is that solution is at least one in boric acid, calcium chloride solution.
Further, the described crosslinking agent of step (2) 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, described in step (2), add the NaSO that solid-liquid is mass concentration 3～10wt%
4solution.
Further, the described acid solution of step (3) is finite concentration HCl or HNO
3the one of solution.
Further, the described reducing solution of step (3) is certain density NaBH
4the aqueous solution.
Advantage of the present invention and beneficial effect:
1) use biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano particle, can be in retaining nano material efficient disposal ability, lower the bio-toxicity of nano-scale, and subtract greatly less granular loss, thereby the environmental risk that migration when reducing nano material and using, conversion process bring;
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 in actual applications simple grid device, just can reach the effect separating completely, is 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, has expanded the scope of application;
3) the pre-treatment way of embedding iron material bead has been proposed in the present invention, wherein acidification step strengthens the physical property of immobilized spherule greatly, through the bead of acidification, when volume reduces slightly, mechanical strength, elasticity etc. are increased, can holding structure in long-term concussion is processed complete.Reduction step is used after acidification step, can ensure zero-valent iron particle partially oxidized in embedding in early stage and acidification again to revert to zero-valent state, strengthens the chemical treatment efficiency of bead.
Brief description of the drawings
Fig. 1 is according to the embodiment of the present invention, the transmission electron microscope picture of the Zero-valent Iron-tri-iron tetroxide double nano material obtaining;
Fig. 2 is according to the embodiment of the present invention, the contrast photo of the biomaterial bead of the not embedding obtaining and embedding iron double nano material;
Fig. 3 is according to the embodiment of the present invention, and biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano bead of preparation is in pretreatment process (under a moisture state; B natural drying after) variation comparison diagram, in b after acidification natural drying bead be 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 embodiment.
In the following example, method therefor if no special instructions, is conventional method.Needed material or reagent in the following example, be if no special instructions market 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) take 0.745g FeCl
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, make reaction system be alkalescence to pH be more than 11; aging 2 hours of constant temperature; make nano ferriferrous oxide granule, after separating, washing, transfer in 1L there-necked flask, add and contain 0.375gFeSO
47H
2the 400mL deionized water solution of O, constant temperature stirs, and dropwise drips and contains 0.35g NaBH
4100mL deionized water solution, react after 1 hour, magnetic separates, and to neutral, obtains Zero-valent Iron-tri-iron tetroxide double nano material with deionized water washing.
(2) taking 5.0g polyvinyl alcohol and 1.5g sodium alginate is dissolved in respectively in 50mL deionized water, 60 DEG C of heating, after dissolving completely, both are uniformly mixed to form to gel, be cooled to room temperature, add step (1) to prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and standing 30min; Then, the aqueous solution that preparation contains concentration 5wt% boric acid and 1.5wt% anhydrous calcium chloride, as crosslinking agent, is drawn above-mentioned iron content biogel with syringe, is added drop-wise in crosslinking agent, and vibration is also preserved after 12 hours in crosslinking agent, transfers to the NaSO of 6wt%
4solution is reinforced.Finally, with deionized water washing, make embedding bead.
(3) the embedding bead of being prepared by step (2) to gained is placed in 1.0mol/L hydrochloric acid solution, and 30 DEG C, 120 revs/min constant temperature water baths vibrations were taken out after 15 minutes, washed with de-ionized water; Then, acidifying bead is added to 0.05mol/L NaBH
4in solution, reduce processing, 30 DEG C, 120 revs/min constant temperature water baths vibrations were taken out after 30 minutes, with deionized water rinsing, made stability and high efficiency biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead.
Fig. 1 is Zero-valent Iron-tri-iron tetroxide double nano material of preparing according to above step and the projection Electronic Speculum picture of embedding bead, and in double nano material, zero-valent iron particle size is in 100 nanometers left and right, and the particle of around less 10-30 nanometer left and right is tri-iron tetroxide.Fig. 2 bead after above-mentioned Zero-valent Iron-ferriferrous oxide material that has been pure polyvinyl alcohol-sodium alginate bead and embedding, bead becomes ater from pure white, illustrates that iron material is mixed and is embedded in biomaterial uniformly.
Take polyvinyl alcohol-sodium alginate to embed Zero-valent Iron-tri-iron tetroxide bead that 8.0g is prepared by above step, join in the Cr that 100mL concentration is 5-40mg/L (VI) aqueous solution, the initial pH of regulator solution is 3.0-11.0,30 DEG C, 150 revs/min of constant temperature water bath vibrations of rotating speed, react.Sampling at regular intervals,
By measuring Cr (VI) content after 0.45 μ m membrane filtration, and calculate clearance, computing formula is as follows:
Wherein: η % is the clearance of t moment system to Cr (VI); C
0for the initial concentration of Cr (VI), mg/L; C
tfor Cr (VI) is at the concentration in t moment, mg/L.
Table 1 be this spherula to tie up to initial pH be under 5.0 conditions, 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, is increased to 18 hours but reach completely the time of removing from 1 hour, and Cr (VI) to the 40mg/L clearance in 24 hours is in 89.3% left and right.
The removal effect of embedding bead 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 be this spherula to tie up to initial concentration be in 10mg/L Cr (VI) solution, the removal effect under different pH condition.Obviously, under acid condition, remove best results, along with the rising of pH, removal efficiency reduces gradually.In the time that pH rises to 11.0, in 12 hours, the clearance of system is only 76.3%.
The removal effect of embedding bead 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 removed the impact of ability on making bead, and concrete steps are as follows:
Embodiment 2-10 adopts different proportion polyvinyl alcohol (PVA) and sodium alginate (SA) to prepare 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 material rate and corresponding removal efficiency are 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 of preparing bead is large, because viscosity is high, drips ball difficulty, and bead easily trails, because optimal proportion is still advisable with 1.5:5.
Embodiment 11-17 adopts different pre-treatments step (different acidifyings and recovery time) to process embedding bead, and uses it for and 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, the impact of pre-treatment step on bead performance, the diafiltration situation of iron and recycling situation in bead use procedure, concrete steps are as follows:
1) by according in embodiment 1 step, prepare without pre-treatment bead, the bead of acidification bead, three kinds of states of acidifying+reduction bead only, the water bath with thermostatic control vibration case that is placed in respectively 30 DEG C, 150 revs/min is cultivated, percentage of damage in research process, to characterize its mechanical strength.Another is organized to bead air-dry under field conditions (factors), the situation of change of bead in research process simultaneously;
2) 8.0g is joined to 100mL containing in Cr (VI) aqueous solution of 20mg/L through 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, the variation of concentration of iron in system in research removal process;
3) under the identical condition of step (2), react after 24 hours, isolate bead, after rinsing well, re-start the pre-treatment step described in the present invention, to the bead processing of regenerating.The bead of having regenerated, after washes clean, recycles, and measures the removal efficiency that at every turn recycles middle Cr (VI)., use without Zero-valent Iron-tri-iron tetroxide system of embedding as a control group meanwhile, recycle test simultaneously.
Result shows, embedding bead is after experience acidification, and mechanical performance improves greatly, in the incubation of 15 days without any Fragmentation Phenomena, and without the almost fragmentation completely within a week of the embedding bead of pre-treatment.Fig. 3 (a) is the cosmetic variation figure that uses bead in pretreatment process of the present invention, and when acidified processing, the volume of bead obviously dwindles, 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 the bead that does not carry out pre-treatment, structural breakdown, embedded material is separated out.If but process without reduction, little club becomes yellow, illustrates that inner iron is easily oxidized, and this process has been avoided in reduction processing, thus be conducive to improve the electronation performance of bead.
Table 5 shows, in use, in solution, iron content can be controlled in 2-3mg/L embedding system under normal circumstances, illustrates that iron diafiltration ratio from bead is lower, and the migration of iron is inhibited.
The infiltration capacity of table 5 embedding bead Fe in Cr (VI) removal course of reaction
| 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 in solution (II) content (mg/L) | 0.2 | 0.2 | 0.5 | 0.3 | 0.6 | 0.2 | 0.3 | 0.2 |
| Fe in solution (III) content (mg/L) | 1.9 | 1.8 | 1.3 | 1.1 | 0.8 | 0.9 | 0.6 | 0.6 |
Table 6 is contrasts of reusing embedding system and independent Zero-valent Iron-tri-iron tetroxide double nano system in aerobic environment, result shows, embedding system still can keep 69.8% clearance in the 4th time uses, and pure system is in the time being used for the third time, clearance is just reduced in 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 separable by salvaging or grid device, and water outlet is limpid, no suspended substance, and need externally-applied magnetic field to assist to separate without 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 are to the contrast of Cr (VI) recycling removal effect
| Cycle-index | For the first time | For the second time | For the third time | The 4th time |
| Zero-valent Iron-tri-iron tetroxide | 96.3% | 68.6% | 49.7% | -- |
| Embedding iron bead | 100% | 88.9% | 84.2% | 69.8% |
Prove by embodiment, the prepared biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system bead of the present invention has good Cr (VI) removal ability.Preparation process is simple, mild condition, and easy controlled operation, the system convenient separation of simultaneously preparing, recycling rate of waterused is high, and environmental friendliness is a kind of nano zero valence iron improving technology preferably, has broad application prospects.
Claims (9)
1. preparation method and the pre-treatment way of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system, it is characterized in that: make 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 embedding bead is carried out to acid treatment and reduction processing, obtain biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead.
2. preparation method and the pre-treatment way of a kind of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system according to claim 1, is characterized in that, specifically comprises the steps:
(1) prepare Zero-valent Iron-tri-iron tetroxide double nano material: first, under nitrogen protection, in there-necked flask, add Fe (III) and Fe (II) molysite, add thermal agitation, after being fully dissolved in deionized water, dropwise drip alkaline solution, regulation system pH is to alkalescence, aging 2～4 hours of constant temperature, makes nano ferriferrous oxide granule, and separating, washing is placed on another there-necked flask; Then, add Fe (II) solution, constant temperature stirs, and dropwise drips excessive reducing solution, reacts after 1 hour, and magnetic separation, to neutral, obtains Zero-valent Iron-tri-iron tetroxide double nano material with deionized water washing.
(2) prepare embedding bead: first, bioencapsulation material heating for dissolving, in 50mL deionized water, is uniformly mixed to form to gel, is cooled to room temperature, add step (1) to prepare gained Zero-valent Iron-tri-iron tetroxide double nano particle, stir and standing 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, reinforces; Finally, with deionized water washing, make embedding bead.
(3) embedding bead pre-treatment step: first, step (2) is prepared to gained embedding bead 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, acidifying bead is added in reducing solution, 30 DEG C of constant temperature water bath vibrations were taken out after 15～45 minutes, with deionized water rinsing, made biomaterial embedding Zero-valent Iron-tri-iron tetroxide bead of stability and high efficiency.
3. preparation method and the pre-treatment way of a kind of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system according to claim 1 and 2, is characterized in that: the described Fe of step (1) (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, is dissolved in the molar concentration rate Fe in deionized water
3+: Fe
2+=2.0～1.6:1.
4. 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 1-3, it is characterized in that: the described alkaline solution of step (1) is the one of ammoniacal liquor or NaOH solution, and described reducing solution is NaBH
4the aqueous solution.
5. 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 1-4, 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.
6. 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 1-5, it is characterized in that: 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.
7. 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 1-6, it is characterized in that: the described cross-linking agent solution of step (2) is at least one in boric acid, calcium chloride solution.
8. preparation method and the pre-treatment way of a kind of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system according to claim 7, it is characterized in that: the described crosslinking agent of step (2) 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.
9. 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 1-8, it is characterized in that: what step (2) was described adds the NaSO that solid-liquid is mass concentration 3～10wt%
4solution.10, 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 1-9, it is characterized in that: the described acid solution of step (3) is finite concentration HCl or HNO
3the one of solution, described reducing solution is certain density NaBH
4the aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069833.3A CN103862037B (en) | 2014-02-27 | 2014-02-27 | The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069833.3A CN103862037B (en) | 2014-02-27 | 2014-02-27 | The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103862037A true CN103862037A (en) | 2014-06-18 |
| CN103862037B CN103862037B (en) | 2015-10-28 |
Family
ID=50901389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410069833.3A Expired - Fee Related CN103862037B (en) | 2014-02-27 | 2014-02-27 | The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103862037B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104439270A (en) * | 2014-09-04 | 2015-03-25 | 河南城建学院 | Method for preparing sodium alginate/beta-cyclodextrin collaborative immobilized nanometer zero-valent iron |
| CN104475749A (en) * | 2014-09-04 | 2015-04-01 | 河南城建学院 | Preparation method of beta-cyclodextrin stabilized embedded nanoscale zero-valent iron |
| CN104722279A (en) * | 2015-03-14 | 2015-06-24 | 河南城建学院 | Method for removing heavy metal cadmium and lead pollutants in water by sodium alginate/gelatin coated nano zero-valent iron |
| CN105251995A (en) * | 2015-11-05 | 2016-01-20 | 北京化工大学 | Preparation method for slow-release-type nanometer zero-valent iron particles |
| CN105771148A (en) * | 2016-03-04 | 2016-07-20 | 华南师范大学 | Nanometer Fe<0>@Fe3O4 composite material and preparation method and application thereof |
| CN105925560A (en) * | 2016-06-29 | 2016-09-07 | 华南理工大学 | Embedded nano iron/two microbial agents and preparation method thereof |
| CN107010708A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of algal polysaccharides sulfuric ester cladding nano zero valence iron and preparation method and application |
| CN107467672A (en) * | 2017-06-27 | 2017-12-15 | 福格森（武汉）生物科技股份有限公司 | A kind of preparation method of ferrous composite gel microsphere |
| CN108015270A (en) * | 2017-12-01 | 2018-05-11 | 南京大学 | A kind of composite iron powder and preparation method and application |
| CN111151226A (en) * | 2020-01-10 | 2020-05-15 | 湘潭大学 | Preparation method and application of copper-iron-carbon nanogel pellets |
| CN112680485A (en) * | 2021-01-20 | 2021-04-20 | 江南大学 | Method for converting L-valine into alpha-ketovaline by immobilized recombinant escherichia coli |
| CN113264575A (en) * | 2021-05-07 | 2021-08-17 | 河南师范大学 | Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material |
| CN113664214A (en) * | 2021-08-06 | 2021-11-19 | 浙江双良商达环保有限公司 | Nano zero-valent iron filler, preparation method thereof and application thereof in denitrification |
| CN115072854A (en) * | 2022-07-07 | 2022-09-20 | 浙江工业大学 | Method for removing triclosan in water by using nano zero-valent iron-ferroferric oxide composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730523A (en) * | 2005-08-26 | 2006-02-08 | 浙江大学 | Method for preparing ordered ferriferrous oxide/chitosan nanometre composite material |
| CN1803634A (en) * | 2006-01-23 | 2006-07-19 | 浙江大学宁波理工学院 | Method for preparing nanometer porous magnetic composite ferroferric oxide material |
| CN101830516A (en) * | 2010-05-18 | 2010-09-15 | 浙江大学 | Method for preparing nano ferroferric oxide particles |
| CN103341165A (en) * | 2013-05-31 | 2013-10-09 | 上海师范大学 | Fe@Fe3O4 nanoparticles having photothermal function, and preparation method and application thereof |
| JP2013546162A (en) * | 2010-09-29 | 2013-12-26 | 清華大学 | Composite soft magnetic powder, composite soft magnetic powder core and method for producing them |
-
2014
- 2014-02-27 CN CN201410069833.3A patent/CN103862037B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730523A (en) * | 2005-08-26 | 2006-02-08 | 浙江大学 | Method for preparing ordered ferriferrous oxide/chitosan nanometre composite material |
| CN1803634A (en) * | 2006-01-23 | 2006-07-19 | 浙江大学宁波理工学院 | Method for preparing nanometer porous magnetic composite ferroferric oxide material |
| CN101830516A (en) * | 2010-05-18 | 2010-09-15 | 浙江大学 | Method for preparing nano ferroferric oxide particles |
| JP2013546162A (en) * | 2010-09-29 | 2013-12-26 | 清華大学 | Composite soft magnetic powder, composite soft magnetic powder core and method for producing them |
| CN103341165A (en) * | 2013-05-31 | 2013-10-09 | 上海师范大学 | Fe@Fe3O4 nanoparticles having photothermal function, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGYUN NIU ETAL.: "Fast defluorination and removal of norfloxacin by alginate/Fe@Fe3O4 core/shell structured nanoparticles", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475749A (en) * | 2014-09-04 | 2015-04-01 | 河南城建学院 | Preparation method of beta-cyclodextrin stabilized embedded nanoscale zero-valent iron |
| CN104439270A (en) * | 2014-09-04 | 2015-03-25 | 河南城建学院 | Method for preparing sodium alginate/beta-cyclodextrin collaborative immobilized nanometer zero-valent iron |
| CN104722279B (en) * | 2015-03-14 | 2018-11-27 | 河南城建学院 | A kind of method that sodium alginate/glutin cladding nano zero valence iron removes heavy metal cadmium, land pollutant in water removal |
| CN104722279A (en) * | 2015-03-14 | 2015-06-24 | 河南城建学院 | Method for removing heavy metal cadmium and lead pollutants in water by sodium alginate/gelatin coated nano zero-valent iron |
| CN105251995A (en) * | 2015-11-05 | 2016-01-20 | 北京化工大学 | Preparation method for slow-release-type nanometer zero-valent iron particles |
| CN105251995B (en) * | 2015-11-05 | 2017-10-10 | 北京化工大学 | A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type |
| CN105771148A (en) * | 2016-03-04 | 2016-07-20 | 华南师范大学 | Nanometer Fe<0>@Fe3O4 composite material and preparation method and application thereof |
| CN105771148B (en) * | 2016-03-04 | 2019-05-28 | 华南师范大学 | A kind of nanometer Fe0@Fe3O4Composite material and preparation method and application |
| CN105925560A (en) * | 2016-06-29 | 2016-09-07 | 华南理工大学 | Embedded nano iron/two microbial agents and preparation method thereof |
| CN105925560B (en) * | 2016-06-29 | 2020-06-19 | 华南理工大学 | Embedded nano-iron/two microbial agents and preparation method thereof |
| CN107010708B (en) * | 2017-04-21 | 2021-02-19 | 山东大学 | Algal polysaccharide sulfate coated nano zero-valent iron and preparation method and application thereof |
| CN107010708A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of algal polysaccharides sulfuric ester cladding nano zero valence iron and preparation method and application |
| CN107467672A (en) * | 2017-06-27 | 2017-12-15 | 福格森（武汉）生物科技股份有限公司 | A kind of preparation method of ferrous composite gel microsphere |
| CN107467672B (en) * | 2017-06-27 | 2020-11-13 | 福格森（武汉）生物科技股份有限公司 | Preparation method of ferrous composite gel microspheres |
| CN108015270A (en) * | 2017-12-01 | 2018-05-11 | 南京大学 | A kind of composite iron powder and preparation method and application |
| CN111151226A (en) * | 2020-01-10 | 2020-05-15 | 湘潭大学 | Preparation method and application of copper-iron-carbon nanogel pellets |
| CN111151226B (en) * | 2020-01-10 | 2022-10-11 | 湘潭大学 | Preparation method and application of copper-iron-carbon nanogel pellets |
| CN112680485A (en) * | 2021-01-20 | 2021-04-20 | 江南大学 | Method for converting L-valine into alpha-ketovaline by immobilized recombinant escherichia coli |
| CN113264575A (en) * | 2021-05-07 | 2021-08-17 | 河南师范大学 | Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material |
| CN113664214A (en) * | 2021-08-06 | 2021-11-19 | 浙江双良商达环保有限公司 | Nano zero-valent iron filler, preparation method thereof and application thereof in denitrification |
| CN113664214B (en) * | 2021-08-06 | 2023-09-29 | 浙江双良商达环保有限公司 | Nanometer zero-valent iron filler, preparation method thereof and application thereof in denitrification |
| CN115072854A (en) * | 2022-07-07 | 2022-09-20 | 浙江工业大学 | Method for removing triclosan in water by using nano zero-valent iron-ferroferric oxide composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103862037B (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103862037B (en) | The preparation of biomaterial embedding Zero-valent Iron-tri-iron tetroxide double nano system and pre-treatment way | |
| CN103599751B (en) | The preparation method of thiol-functionalizedmagnetic magnetic silica nano-material | |
| CN111790422B (en) | Graphitized nitrogen-complexed Fe (III) -Fe0Catalyst, and synthesis method and application thereof | |
| CN101402485B (en) | Cohesive action nutrient source SRB sewage sludge immobilization particle, production and uses in treating heavy metal wastewater thereof | |
| CN104059167B (en) | A kind of preparation method and applications of polyamine compounds modified magnetic chitosan | |
| CN103877927B (en) | Magnetic Nano Fe 3o 4living things catalysis prepares method and the application in uranium-containing waste water process thereof | |
| CN102258980B (en) | Method for preparing sulfured magnetic chitosan and method for treating waste water containing heavy metals by using sulfured magnetic chitosan | |
| CN106636057A (en) | Nutrient source immobilized sulfate reducing bacterium globules as well as preparation method and application thereof | |
| CN109876779B (en) | Nano mesoporous Fe 3 O 4 Preparation and application of-chitosan core-shell crosslinked microsphere material | |
| CN104941610A (en) | Preparation and application of magnetic hydrogel loaded with one-dimensional Fe3O4 nanocrystals | |
| CN105668757A (en) | Graphene/sodium alginate globules modified by nano zero-valent iron and preparing method and application thereof | |
| CN112791714B (en) | Magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, preparation method and application | |
| CN113943030B (en) | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof | |
| CN104607228A (en) | Preparation method for alpha-Fe2O3 quantum dot/nitrogen-doped graphene composite material | |
| CN108017793A (en) | A kind of application being sustained in the preparation method and its chemical wastewater treatment of polyurethane mesh carrier | |
| CN108330123A (en) | A kind of preparation method of denitrogenation embedded immobilization particle | |
| CN106423088A (en) | Preparation and application of novel functional magnetic graphene oxide composite material | |
| CN109954518A (en) | A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method and device | |
| CN104045129B (en) | A kind of preparation method removing the Nanoscale Iron charcoal micro-electrolysis material of nitrate nitrogen | |
| CN102101729B (en) | Method for removing heavy metal pollutant from water body by using phanerochete chrysosporium | |
| CN111686703A (en) | Remove aquatic Cs+Composite microcapsule adsorbent and preparation method thereof | |
| CN106676091A (en) | Preparation method of immobilized microorganism spherules | |
| CN108786723A (en) | Utilize the method for estrogen in activation montmorillonite biology carbon composite removal water body | |
| CN113441142A (en) | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst | |
| CN105772020B (en) | A kind of preparation method of the additive Mn magnetic ferrites microballoon with good Fenton catalytic performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20190227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |