CN104907057A - Spinning immobilized carbonyl iron material and application thereof in water treatment - Google Patents
Spinning immobilized carbonyl iron material and application thereof in water treatment Download PDFInfo
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Abstract
The invention discloses a spinning immobilized cage-like carbonyl iron nano particle and application of the spinning immobilized cage-like carbonyl iron nano particle. The electrostatic spinning technology is adopted to immobilize a cage-like carbonyl iron material to prepare the spinning immobilized carbonyl iron material, and dissolved heavy metal ions in water are removed in an adsorption mode. The prepared adsorbing agent has high adsorption rate, the concentrations of heavy metal antimony and selenium are reduced to be lower than the limit value of the concentrations of drinking water when the adsorbing agent is added, more than 95% of heavy metal antimony and selenium are removed within 100min, and 97% of arsenic can be removed within 150min. The adsorption rate of the adsorption material is considerably higher than that of the other composite adsorbing materials, and the adsorbing effect of the adsorbing agent is stable; compared with other treatment modes, the method can shorten the reaction time and the treatment expenses; the spinning immobilized cage-like carbonyl iron nano particle has excellent separation property, water body after adsorption treatment is not required to be filtered and separated, and the heavy metal adsorption removal technology is particularly suitable for large-scale industrialized application.
Description
Technical field:
The invention belongs to heavy metal in water ion remaval technical field, particularly a kind of caged iron carbonyl material of being fixed by electrostatic spinning technique and the removal to the common high toxicity heavy metal of water body thereof.
Background technology:
In recent years, along with China's develop rapidly industrially, the environmental problem day by day increased the weight of also is subject to increasing attention.Particularly along with high concentration, high toxicity heavy metal is due to discharge beyond standards and be not good at disposing, and the accumulation in surface water and underground water, the health and safety of the mankind in serious threat.Arsenic, antimony, selenium are as heavy metal common in polluted-water, extensively exist in the trade effluent of mining, pigment and dyestuff processing and other fields, cause content of beary metal severe overweight in industrial water drainage, have a strong impact on the water quality of peripheral ground water and underground water and the safety of neighbouring drinking water source.In addition, in the drinking water source water body in some areas also there is the phenomenon exceeded standard in content of beary metal.The heavy metal how retained in cost-effective removal water body, reduces industrial water drainage and has become current water environment field problem demanding prompt solution to the threat of ecological environment.
Present stage, the precipitation method, oxidation-reduction method, ion-exchange, bioanalysis and absorption method etc. are mainly contained to the minimizing technology of heavy metal in environment.Consider, the feature that absorption method is cheap, efficient, stable, the advantages such as applicable elements is extensive, simple to operate, become the prefered method of industrial heavy metal in water purification.But we find in actual applications, common adsorbents exists that adsorption capacity is little, absorption stability is poor, adsorption time is long, treatment effect is vulnerable to ambient conditions as pH, the impact of temperature and coexisting ion etc., and adsorbent adds rear needs carries out after-treatment to water body after absorption, adds the operation of water body purification process.Based on above problem, novel, easily separated and the sorbing material that adsorption effect is good has become the emphasis urgently developed.
Electrostatic spinning technique is material preparation technology solution or melt substance being changed into continuous print, the continuous rope of diameter between several microns to a few nanometer general at present.The method of operating of electrostatic spinning technique is simple, preparation cost is cheap, and obtained spinning film has larger specific area, stable in properties, is easy to the advantages such as separation and recovery.Meanwhile, the functional particles that inorganic salts etc. can be had different shape by this technology is combined on polymer fiber with higher concentration, and has broad application prospects in the preparation field of composite.The composite cellulosic membrane sorbing material of development based on electrostatic spinning technique, has shown good absorption property to heavy metal pollutants in water, to common heavy metal polluter Cu
2+, Cd
2+, As
5+deng adsorption capacity can reach 161.29mg/g respectively, 357.14mg/g (Wang X.F., et al., Poly (ethyleneimine) nanofibrous affinity membrane fabricated via one step wet-electrospinning from poly (vinyl alcohol)-doped poly (ethylenemine) solution system and its application [J] .Journal of Membranes Science, 2011, 397, 191-120) 7.1mg/g (Min L L., et al., Preparation of a novel iron oxide/chitosan composite nanofiber and its adsorption of arsenate from water [J] .Acta Scientiae Circumstantiae, 2014, 34 (12), 2979-2984).From the adsorption effect of existing composite fiber membrane material to heavy metal in water, electrostatic spinning nano fiber film can effectively be removed by heavy metal polluter really, but removes speed and adsorption capacity has much room for improvement.This just requires that the sorbing material selecting to have higher adsorption activity and spinning fibre carry out more efficiently combination, is also the research emphasis preparing easily separated adsorption cleaning material.
Tradition sorbing material---iron carbonyl, the absorption property good because of it and character cheap and easy to get and industrially extensive use.But traditional iron carbonyl closely structure can serious limit pollution thing to its internal migration, reduce the contact in adsorbate and its surface-active site.From structure angle, the active adsorption sites on its surface not only can effectively discharge by the sorbing material of lamellar structure, and the specific area of material can be increased largely, adsorbate in solution is fully contacted with the avtive spot of adsorbent surface, improves its absorption property.Therefore, a kind of caged iron carbonyl material of etching template synthesis that adopts is incorporated in the preparation of spinning fibre film by we, make full use of the adsorption capacity of avtive spot raising spinning fibre film in heavy metal adsorption that this iron carbonyl material enriches, remove rapidly, efficiently to realize spinning membrane material heavy metal.
In sum, this fiber film material combined with electrostatic spinning by caged iron carbonyl material is with the double dominant of caged material and membrane material: the hydroxyl of iron carbonyl material surface not only can be made to be fully used, add the active adsorption sites of material surface largely, can ensure that again this composite has excellent separating property, avoid the after-treatment of adsorbing rear water body.This composite fiber membrane material obtains good adsorption effect in heavy metal in water adsorption cleaning field, solves largely in engineering and commercial Application and removes to heavy metal in water purification the problem being difficult to adsorbent be separated.
Summary of the invention
In order to solve the problem, the present invention adopts the method preparative separation function admirable be fixed on by caged iron carbonyl nano particle on spinning fibre film, sorbing material that absorption property is good, and deep purifying removal is carried out to arsenic, antimony, selenium three kinds of heavy metal in waters, below the concentration of making every effort to industrial water drainage be reduced to the concentration of this three heavy metal species in drinking water resource defined in " Drinking Water quality standard " (GB5749-2006), with the potential threat solving arsenic, antimony, this three heavy metal species material of selenium exist surrounding environment and health.Reduce processing cost and intractability, avoid adsorbing rear water body after-treatment while ensure adsorption treatment after water outlet reach water quality standard for drinking water.
For achieving the above object, the present invention proposes the method be fixed to by caged iron carbonyl nano particle on spinning fibre film, and body step is as follows:
(1) preparation of caged iron carbonyl:
First 3.8g polyvinylpyrrolidone being dissolved under the effect of magnetic stirring apparatus 50mL concentration is in 0.1mol/L watery hydrochloric acid, to be dissolved completely after, 110mg potassium ferrocyanide is added in above-mentioned mixed liquor, is stirred to formation settled solution.Again this settled solution is transferred in 80 DEG C of constant temperature ovens and reacts 24h, can be observed blue deposit and generate.The deposit of gained after isothermal reaction is transferred in centrifuge tube, after centrifugal, outwells supernatant, obtain pure blue deposit and be pure ferric ferrocyanide.
In the blue deposit of above-mentioned gained, add ultra-pure water, and deposit is scattered in completely in ultra-pure water under ultrasound condition.Again through centrifugal remove supernatant after, in deposit, add absolute ethyl alcohol, make that deposit breakup is again centrifugal after ethanol removes supernatant through ultrasonic.
Add absolute ethyl alcohol in the most backward blue deposit, ultrasonicly make it disperse completely, then the sodium hydroxide solution being 0.2mol/L by itself and 50mL concentration mixes.Be placed on rotary shaker after hybrid reaction 12h by this mixed solution, the blue ferric ferrocyanide deposit preparing gained is transformed into crocus gradually, and the precipitation through centrifugal gained is caged iron carbonyl nano particle.
(2) electrostatic spinning technique fixes the preparation of caged iron carbonyl:
First polyacrylonitrile is added in DMF, under the effect of magnetic agitation, make it dissolve completely, obtain precursor liquid; Caged iron carbonyl nano particle step (1) obtained subsequently, through centrifugal post-drying, thoroughly removes moisture; The caged iron carbonyl material of drying is joined in above-mentioned precursor liquid, under the effect of magnetic agitation, makes it mix, obtain the spinning solution containing caged iron carbonyl.Finally spinning solution is injected in the syringe with draw point, and is connected with high-pressure spinning machine.Spray via high-pressure spinning machine the filiform obtained and be the spinning material combining caged iron carbonyl, also namely final required through electrostatic spinning immobilized caged iron carbonyl material.
Described polyacrylonitrile consumption is 0.7-1g;
Described DMF consumption is 5-15mL;
Described caged iron carbonyl dosage is 0.05-0.1mg;
Beneficial effect:
1) the present invention adopts the technology of electrostatic spinning to be fixed by caged iron carbonyl material first, prepares spinning immobilization iron carbonyl material.The heavy metal ion of solubilised state in water is removed by the mode of absorption.
2) sorbing material prepared by the present invention has higher adsorption capacity and the rate of adsorption faster, in 100min, heavy metal antimony, selenium can be removed more than 95%, in 150min, arsenic be removed 97%.The adsorption capacity of this sorbing material is far above other composite adsorbing materials, and treatment effect is stablized; Compared with other processing modes, reduce reaction time and disposal cost.
3) sorbing material prepared by the present invention is film-form, can directly take out from process water body after a procedure, there is excellent separating property, avoid the isolated by filtration of dispersed sorbing material in the rear water body of process, make the technology of Adsorption heavy metal be more suitable for industrialization large-scale application.
Accompanying drawing explanation
Fig. 1 caged iron carbonyl prepares the electron microscopic picture of predecessor ferric ferrocyanide;
The electron microscopic picture of Fig. 2 caged iron carbonyl;
The transmission electron microscope picture of Fig. 3 caged iron carbonyl;
Fig. 4 is fixed on the caged iron carbonyl electron microscopic picture on electrostatic spinning;
The immobilized caged iron carbonyl of Fig. 5 is to the adsorption effect of heavy metal in water
Wherein, (a) is pentavalent arsenic, and (b) is trivalent antimony, and (c) is tetravalence selenium;
Wherein, solid line is Freundlich Adsorption Model dotted line is Langmuir Adsorption Model;
Fig. 6 immobilized caged iron carbonyl heavy metal pollutes the treatment effect of actual water body
Wherein, (a) is trivalent arsenic+pentavalent arsenic, and (b) is trivalent antimony, and (c) is tetravalence selenium
Detailed description of the invention
Embodiment 1: a kind of preparation method of caged iron carbonyl
1, the preparation of caged iron carbonyl:
At ambient temperature, first 3.8g PVP K-30 is dissolved under the effect of magnetic stirring apparatus in 50mL 0.1mol/L watery hydrochloric acid, to be dissolved completely after, 110mg potassium ferrocyanide is added in above-mentioned mixed liquor, continue to stir 30min, until form settled solution.Again this settled solution is transferred in 80 DEG C of constant temperature ovens and reacts 24h, blue deposit can be observed and generate.The deposit of gained after isothermal reaction is transferred in centrifuge tube, under 7500rpm, outwells supernatant after centrifugal 15min, obtain pure blue deposit.In the blue deposit of above-mentioned gained, add ultra-pure water, and deposit is scattered in completely in ultra-pure water under ultrasonic adjustment.Under 7500rpm condition, outwell supernatant after centrifugal 15min again, add absolute ethyl alcohol subsequently in deposit, through the ultrasonic deposit breakup that makes after ethanol, centrifugal 15min under 7500rpm again.Final removing supernatant, the blue deposit of gained is pure ferric ferrocyanide.In the blue deposit of gained, add 10ml absolute ethyl alcohol, ultrasonicly make it disperse completely, then it is mixed with 50mL 0.2mol/L NaOH.Be placed in by this mixed solution after rotary shaker mixes 12h, the blue ferric ferrocyanide deposit preparing gained is transformed into crocus gradually, more just can obtain caged iron carbonyl nano particle after the centrifugal 15min of 7500rpm.
Fig. 1 is the electron microscopic picture of the predecessor ferric ferrocyanide of caged iron carbonyl prepared by embodiment 1, obviously can observe the well-regulated cubic shaped of ferric ferrocyanide tool preparing gained from figure, and arrangement is loose, and size is homogeneous, and degree of scatter is better.
Fig. 2 is the electron microscopic picture of caged iron carbonyl nano particle prepared by embodiment 1, can find out that the etching of NaOH does not destroy the cubic morphology of material, and the surface of otherwise smooth becomes loose, is conducive to contacting with the polluter in water body.
Fig. 3 is the transmission electron microscope picture of caged iron carbonyl prepared by embodiment 1, this material can be observed and present loose hollow structure on a microscopic level, confirm the cube structure of the rule that caged iron carbonyl is made up of five compact siro spinning technology lamella together further.
Embodiment 2: a kind of electrostatic spinning fixes the preparation method of caged iron carbonyl
First will prepare caged iron carbonyl material high speed centrifugation 2min under 10000rpm of gained in embodiment 1, wherein remaining moisture is thoroughly removed; Secondly, 800mg polyacrylonitrile is joined in 10mL DMF, under the effect of magnetic agitation, polyacrylonitrile dissolved completely, mix, as the precursor liquid of spinning solution; Subsequently, 0.1mg is mixed with above-mentioned precursor liquid through the caged iron carbonyl of centrifugal segregation moisture, under magnetic agitation condition, make it continue to mix; Finally, the spinning solution containing caged iron carbonyl is transferred in the syringe being furnished with stainless steel syringe needle, and be assembled on high-pressure spinning machine.Spinning voltage is set as 20KV, and solution is advanced by peristaltic pump, and fltting speed is 1mL per minute.The filiform ejected is the spinning material combining caged iron carbonyl.
Fig. 4 is the electron microscopic picture being fixed on the caged iron carbonyl material on electrostatic spinning of embodiment 2 gained, as can be seen from the figure, caged iron carbonyl material is that string-of-pearls-like is connected in thread spinning, the caged iron carbonyl combined through spinning does not change its basic configuration, and the immobilization of sorbing material can't bring greater impact the absorption property of material.
Embodiment 3: a kind of electrostatic spinning fixes the preparation method of caged iron carbonyl
First will prepare caged iron carbonyl material high speed centrifugation 2min under 10000rpm of gained in embodiment 1, wherein remaining moisture is thoroughly removed; Secondly, 700mg polyacrylonitrile is joined in 5mL DMF, under the effect of magnetic agitation, polyacrylonitrile dissolved completely, mix, as the precursor liquid of spinning solution; Subsequently, 0.05mg is mixed with above-mentioned precursor liquid through the caged iron carbonyl of centrifugal segregation moisture, under magnetic agitation condition, make it continue to mix; Finally, the spinning solution containing caged iron carbonyl is transferred in the syringe being furnished with stainless steel syringe needle, and be assembled on high-pressure spinning machine.Spinning voltage is set as 20KV, and solution is advanced by peristaltic pump, and fltting speed is 1mL per minute.The filiform ejected is the spinning material combining caged iron carbonyl.
Embodiment 4: a kind of electrostatic spinning fixes the preparation method of caged iron carbonyl
First will prepare caged iron carbonyl material high speed centrifugation 2min under 10000rpm of gained in embodiment 1, wherein remaining moisture is thoroughly removed; Secondly, 1000mg polyacrylonitrile is joined in 15mL DMF, under the effect of magnetic agitation, polyacrylonitrile dissolved completely, mix, as the precursor liquid of spinning solution; Subsequently, 0.075mg is mixed with above-mentioned precursor liquid through the caged iron carbonyl of centrifugal segregation moisture, under magnetic agitation condition, make it continue to mix; Finally, the spinning solution containing caged iron carbonyl is transferred in the syringe being furnished with stainless steel syringe needle, and be assembled on high-pressure spinning machine.Spinning voltage is set as 20KV, and solution is advanced by peristaltic pump, and fltting speed is 1mL per minute.The filiform ejected is the spinning material combining caged iron carbonyl.
Embodiment 5: electrostatic spinning immobilized caged iron carbonyl material is to the method for adsorbing and purifying of heavy metal in water
Actual heavy metal-polluted water is simulated with the sewage respectively containing 1mg/L low-concentration arsenic, antimony and selenium three kinds of ions, and immobilized caged iron carbonyl material gained being prepared by embodiment 2 joins in polluted water body, throwing amount is 0.25g/L, regulates solution p H value between 6 ~ 7 with watery hydrochloric acid and dilute sodium hydroxide.Along with the carrying out of reaction, draw a certain amount of mixed solution at significant interval syringe after 0.22 μm of membrane filtration, measure remaining concentration of heavy metal ion in settled solution, and be back-calculated to obtain the heavy metal ion amount of Adsorption.
Fig. 5 is that the obtained spinning immobilization iron carbonyl material of embodiment 2 is to the adsorption effect of arsenic, antimony, selenium.In order to measure prepared spinning immobilization iron carbonyl material to the absorption property of arsenic, antimony, selenium, to show in solution initial concentration and solution initial pH value in figure to the impact of absorption property.As can be seen from the experimental result of different initial pH value, acid condition is conducive to the absorption of arsenic, antimony, selenium.As can be seen from the fitting result of Freundlich and Langmuir two kinds of Adsorption Model, Freundlich model more meets the real process of absorption, illustrates that iron carbonyl is to the chemisorbed process of the absorption of arsenic, antimony, selenium three kinds of materials closer to polymolecular layer.Under saturated adsorption condition, adopt Langmuir curve to carry out matching to absorption result, its fitting result shows, and can reach 250mg/g to the maximal absorptive capacity of As (V); Can up to 2563mg/g to the saturated extent of adsorption of Sb (V); 170mg/g can be reached to the adsorption capacity of Se (IV).
Fig. 6 is that embodiment 2 prepares the spinning immobilization iron carbonyl material of gained to the purified treatment design sketch of the actual water body of simulation respectively containing arsenic, antimony, selenium three heavy metal species polluter.As can be seen from the figure, the concentration of arsenic, antimony, selenium under pH is the condition of 6 ~ 7, can be reduced to reduced levels by immobilized iron carbonyl material in 120min.This result shows, is fixed on by sorbing material on electrostatic spinning and the good absorption property of caged material itself still can be made to be not fully exerted, and can keep the rate of adsorption and preferably adsorption capacity faster to the heavy metal retained in water body.
Contrast with the adsorption effect of existing adsorbent, the spinning immobilization iron carbonyl material that the present invention prepares gained has superior adsorbing heavy metal in water arsenic, antimony, the ability of selenium and good separating property.Main cause is: first, and the caged iron carbonyl material of cube structure has larger specific area and a large amount of surface active groups fully exposed, and effectively can carry out adsorption reaction while lifting with adsorbate contact probability; Secondly, be the advantage that the caged iron carbonyl material that arranges of string-of-pearls-like can retain cage structure largely at spinning surface, make sorbing material main body as much as possible with adsorbate haptoreaction in solution; Finally, the characteristic that static spinning membrane itself is easy to be separated from water is that this sorbing material provides excellent separating property, after avoiding absorption, water body is carried out to the problem of after-treatment.
Electrostatic spinning immobilized caged iron carbonyl material all has the rate of adsorption and larger adsorption capacity faster to arsenic, antimony, selenium in polluted-water, and the preparation flow of material own is simple, low in raw material price, can keep good separating property and mechanical performance in water, be not only industrial extensive use and provide good condition, become the guiding of sorbing material development from now on yet.
Claims (7)
1. a preparation method for spinning immobilization iron carbonyl material, it is characterized in that, concrete steps are as follows:
(1) preparation of caged iron carbonyl:
First 3.8g polyvinylpyrrolidone being dissolved in 50mL concentration is in 0.1mol/L watery hydrochloric acid, to be dissolved completely after, 110mg potassium ferrocyanide is added in above-mentioned mixed liquor, be stirred to formation settled solution, again this settled solution is transferred in 80 DEG C of constant temperature ovens and reacts 24h, generate blue deposit, the pure blue deposit of the centrifugal acquisition of the deposit of gained after isothermal reaction is pure ferric ferrocyanide;
In blue deposit, absolute ethyl alcohol is added again after using pure water and the above-mentioned blue deposit of ethanol washing respectively, ultrasonicly it is made to disperse completely, the sodium hydroxide solution being 0.2mol/L by itself and 50mL concentration again mixes, mixed solution to be placed on rotary shaker after hybrid reaction 12h, the blue ferric ferrocyanide deposit preparing gained is transformed into crocus gradually, and the precipitation through centrifugal gained is caged iron carbonyl nano particle;
(2) electrostatic spinning technique fixes caged iron carbonyl:
First polyacrylonitrile is dissolved completely in DMF, obtain precursor liquid; Caged iron carbonyl nano particle step (1) obtained subsequently, through centrifugal post-drying, thoroughly removes moisture; The caged iron carbonyl material of drying is joined in above-mentioned precursor liquid, mixes, obtain the spinning solution containing caged iron carbonyl; Finally be injected into by spinning solution in the syringe with draw point, and be connected with high-pressure spinning machine, spraying via high-pressure spinning machine the filiform obtained and be the spinning material combining caged iron carbonyl, is also spinning immobilization iron carbonyl material.
2. the preparation method of a kind of spinning immobilization iron carbonyl material as claimed in claim 1, it is characterized in that, described polyacrylonitrile consumption is 0.7-1g.
3. the preparation method of a kind of spinning immobilization iron carbonyl material as claimed in claim 1, it is characterized in that, described DMF consumption is 5-15mL.
4. the preparation method of a kind of spinning immobilization iron carbonyl material as claimed in claim 1, it is characterized in that, described caged iron carbonyl dosage is 0.05-0.1mg
5. the preparation method of a kind of spinning immobilization iron carbonyl material as claimed in claim 1, it is characterized in that, the step that described electrostatic spinning technique fixes caged iron carbonyl is:
(1) caged iron carbonyl material high speed centrifugation 2min under 10000rpm, makes wherein remaining moisture thoroughly remove;
(2) 800mg polyacrylonitrile is joined in 10mL DMF, under the effect of magnetic agitation, polyacrylonitrile dissolved completely, mix, as the precursor liquid of spinning solution;
(3) 0.1mg is mixed with above-mentioned precursor liquid through the caged iron carbonyl of centrifugal segregation moisture, under magnetic agitation condition, make it continue to mix to obtain spinning solution;
(4) spinning solution containing caged iron carbonyl is transferred in the syringe being furnished with stainless steel syringe needle, and be assembled on high-pressure spinning machine, spinning voltage is set as 20KV, solution is advanced by peristaltic pump, fltting speed is 1mL per minute, and the filiform ejected is the spinning material combining caged iron carbonyl.
6. as spinning immobilization iron carbonyl material prepared by any one method of claim 1-5.
7. spinning immobilization iron carbonyl material as claimed in claim 6 is processing the heavy application of heavy metal pollution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105802950A (en) * | 2016-05-24 | 2016-07-27 | 天津工业大学 | Beaded electrospun nanofiber immobilized saccharomycete and preparation method thereof |
| CN106000330A (en) * | 2016-07-06 | 2016-10-12 | 中国科学院生态环境研究中心 | Hollow cubic iron-aluminum composite oxyhydroxide defluorination adsorbent based on electrospining immobilization |
| CN106179231A (en) * | 2016-07-06 | 2016-12-07 | 中国科学院生态环境研究中心 | A kind of hollow cube ferrum aluminum is combined preparation and the application process of oxyhydroxide de-fluoridation adsorbent |
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| EA005782B1 (en) * | 2003-01-17 | 2005-06-30 | Светлана Ивановна Полушкина | Method for removal of heavy metal ions from wastewater |
| CN102921372A (en) * | 2011-08-11 | 2013-02-13 | 同济大学 | Layered hydroxy composite metal oxide, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105802950A (en) * | 2016-05-24 | 2016-07-27 | 天津工业大学 | Beaded electrospun nanofiber immobilized saccharomycete and preparation method thereof |
| CN106000330A (en) * | 2016-07-06 | 2016-10-12 | 中国科学院生态环境研究中心 | Hollow cubic iron-aluminum composite oxyhydroxide defluorination adsorbent based on electrospining immobilization |
| CN106179231A (en) * | 2016-07-06 | 2016-12-07 | 中国科学院生态环境研究中心 | A kind of hollow cube ferrum aluminum is combined preparation and the application process of oxyhydroxide de-fluoridation adsorbent |
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