CN104043409A - Immobilized membrane for synchronously enriching phosphor and ferrum and preparation method thereof - Google Patents
Immobilized membrane for synchronously enriching phosphor and ferrum and preparation method thereof Download PDFInfo
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- CN104043409A CN104043409A CN201310076971.XA CN201310076971A CN104043409A CN 104043409 A CN104043409 A CN 104043409A CN 201310076971 A CN201310076971 A CN 201310076971A CN 104043409 A CN104043409 A CN 104043409A
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Abstract
Provided is an immobilized membrane for synchronously enriching phosphor and ferrum. The immobilized membrane is a gel film which is prepared from a film-forming liquid in a gelling manner, wherein the film-forming liquid comprises zirconium hydroxide hydrate, Chelex-100 cation exchange resin and polyacrylamide. A preparation method of the immobilized membrane includes following steps: fully a mixing zirconium hydroxide hydrate powder, the Chelex-100 cation exchange resin and a polyacrylamide aqueous solution together to obtain a uniform membrane liquid, adding an appropriate amount of Tetramethylethylenediamine and ammonium persulfate, filling a glass mould with the membrane liquid, placing the glass mould horizontally at a low temperature of 2-4 DEG C for enabling zirconium hydroxide hydrate and Chelex to be freely precipitated, performing a heating process to 45+/-5 DEG C and laying the glass mould up until the membrane liquid gels into a membrane. The immobilized membrane can synchronously enrich phosphor and ferrous ions with a high enriching capacity and can be used for a high resolution synchronous analysis of the phosphor and the ferrous ions in an environmental sample.
Description
Technical field
The present invention relates to a kind of diffusive gradients in thin-films technology (Diffusive gradients in thin films, DGT) fixing film in and preparation method thereof, be applicable to the concentration and analysis of phosphorus and iron in surrounding medium, relate in particular to fixing film of synchronous enriched phosphorus and iron in a kind of environmental analysis and preparation method thereof.
Background technology
Phosphorus and iron are all source of students key elements important in water body environment.Phosphorus is the critical limitation element that causes body eutrophication, and the rising of the total phosphorus concentration is the main cause that causes blue-green algae undue growth and algal tufa to form.Iron bound phosphorus is one of main occurrence patterns of phosphorus in deposit and flooded soils.These phosphorus are adsorbed to (hydrogen) iron oxide surface, and in the time that iron oxide is reduced into ferrous iron under anoxia condition, the phosphorus being adsorbed onto on iron oxide will discharge, and cause the secondary pollution of sediment phosphorus to water body.Therefore, research phosphorus and iron coupled relation, be to disclose one of sediment phosphorus pollution course and machine-processed core content, and synchronous high-resolution obtains both space distribution informations, provides important technical support for carrying out correlative study.
To the mensuration of active phosphorus in water body deposit and the iron mode of mainly taking the initiative, after deposit is taken out from water body, send laboratory back to and analyze.Due to deposit under the natural conditions of water body in reducing environment, after taking-up, very easily change, cause analytical error.The passive sampling technology of development at present, as diffusive gradients in thin-films technology, the fixing film that can absorb the element such as phosphorus or iron inserts in deposit, in-situ enrichment phosphorus or iron, after fixing again film and taking out, by analyzing phosphorus or the iron on fixing film, indirectly obtain the information of active phosphorus in deposit or iron.
Diffusive gradients in thin-films technology (Diffusive gradients in thin films, DGT) be that a kind of non-destructive, original position are obtained pollutant distribution and active technology in deposit, fixing film enrichment be can utilize and deposit active phosphorus or iron measured, but in DGT mensuration, the fixing film overwhelming majority used is the fixing film of single absorption function at present, can only absorb phosphorus or iron, synchronously absorption and enriched phosphorus and iron, cause analysis determination efficiency low, and operating cost is high simultaneously.
201210208540X discloses a kind of synchronous enriched phosphorus (PO
4 3-) and sulphur (S
2-) fixing film and preparation method thereof, adopting hydronium(ion) oxidation zirconium (ZrO) and silver iodide is fixative, respectively p and s ion is produced to absorption and precipitation, due to these two kinds not same-action can not produce interference, therefore this synchronously enrichment of fixing film p and s, and single enriching quantity is not subject to the impact of two kinds of fixative stacks.At present, still do not see synchronous fixing phosphorus and iron (Fe
2+) fixing film and preparation method thereof.The phosphorus fixing film of simple function mainly adopts hydronium(ion) oxidation zirconium, iron hydroxide and Metsorb as phosphorus fixation agent, and it is fixative that the ferropexy film of single absorption function adopts Chelex-100 conventionally.Because above-mentioned fixative is all suction-operateds to the fixation principle of phosphorus or iron ion, and absorption object is respectively anion and cation, when their stacks are used for making ferrophosphorus and synchronously fix film, likely produces phase mutual interference, do not reach synchronous fixing effect.
Summary of the invention
The present invention aims to provide fixing film of the synchronous enriched phosphorus of a kind of energy and iron and preparation method thereof, improve DGT technology be applied to water body environment analyze in the determination efficiency of active phosphorus and iron, reduce cost of determination simultaneously.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A fixing film for synchronous enriched phosphorus and iron, is characterized in that, this fixing film is by the film forming liquid that comprises hydronium(ion) oxidation zirconium, Chelex-100 cationic ion-exchange resin and polyacrylamide, the gel film of making after gelling.
Described fixing film surface deposition zirconium hydroxide and Chelex-100 cationic ion-exchange resin.
In described fixing film, the weight ratio of hydronium(ion) oxidation zirconium and Chelex-100 cationic ion-exchange resin is 1:0.6～1:1.
The fixing film of described synchronous enriched phosphorus and iron adopts following methods to make: 1g hydronium(ion) is oxidized to zirconium powder end and 0.6～1g Chelex-100 cationic ion-exchange resin and polyacrylamide solution and fully mixes, make uniform film forming liquid, add after appropriate ammonium persulfate and tetramethyl diethylamine, by in this film forming liquid implantation glass mould, horizontal positioned under 2-4 DEG C of low temperature, make after zirconium hydroxide and Chelex-100 free settling, be warming up to again 45 ± 5 DEG C of placements, the film until film forming sol congeals into.
More specifically and optimally, described method comprises the following steps:
1) rear grinding mixed in the hydronium(ion) oxidation zirconium powder end of 1g moisture content 50 ± 5% and 3～5mL, 30% polyacrylamide solution, add 0.6～1g Chelex-100 cationic ion-exchange resin to mix and obtain film forming liquid;
2) again to the ammonium persulfate and 4～8 μ L tetramethyl diethylamine (TEMED) that add 12～16 μ L 10% (wt) in the film forming liquid of step 1) gained, mix in the space of even thickness between two glass sheets of rear implantation glass mould, bubble is caught up with to the greatest extent;
3) glass mold is under 2-4 DEG C of low temperature more than horizontal positioned half an hour, make hydronium(ion) oxidation zirconium and Chelex-100 Particle free be deposited to bottom (one side is the front of fixing film) downwards, then be warming up to 45 ± 5 DEG C, more than placing half an hour, the film until film forming sol congeals into;
4) take out after gel film, put into deionized water and soak more than 24 hours, make described synchronous enriched phosphorus and the fixing film of iron.
Described hydronium(ion) oxidation zirconium powder end can be prepared by the following method, regulate pH to 7.0 ± 0.2 of the zirconium oxychloride aqueous solution of 0.1M with 25% ammoniacal liquor, the precipitate with deionized water producing is washed till without chlorion, precipitation is after centrifugation, being dried and controlling its moisture content is between 50 ± 5%, then grind into powder.
Advantage of the present invention and beneficial effect comprise:
1) fixing film production process optimization of the present invention, fixing film is all having excellent performance aspect absorption property and physical strength.The fixing film of complex function comprises two kinds of different fixatives, and its production process is different from the fixing film that comprises single fixative, and various parameters need to be explored and optimize.Zirconium hydroxide and Chelex-100 addition and proportioning, the temperature and time of ammonium persulfate and tetramethyl diethylamine addition, the sedimentation of film liquid and gelling etc., for formation and the performance of film, particularly two kinds of adsorbents are in the remarkable impact of being distributed with of film surface.After above-mentioned parameter is optimized, in the preparation process of the fixing film of the present invention, zirconium hydroxide and Chelex-100 can fully be deposited to surface, and form rational distribution on surface, make two kinds of adsorbents reach optimum to the adsorption capacity of phosphorus or iron, fix film simultaneously and can keep stable shape, not yielding, absorbent particles does not come off.
2) compared with the simple function phosphorus fixing film of reporting, two kinds of adsorbents of fixing film of synchronous enriched phosphorus of the present invention and iron have synergy, all have very high enrichment capacity for phosphorus and iron.At Chelex-100 preferentially in film surface distributed, when ensureing iron enrichment capacity, the addition of Chelex-100 does not have significant adverse effect (referring to Fig. 3 B) to phosphorus absorption property, and phosphorus enrichment capacity (>83 μ g P cm-2) is respectively traditional F eO film, modified FeO film and Metsorb film 20 times, more than 6 times and 3.5 times.Due to this advantage, can be by fixing film of the present invention for analyzing the eutrophic lake of high phosphorus background.On the other hand, unexpectedly, fixing film of the present invention is significantly higher than the ferropexy film (referring to Fig. 3 A) of simple function for the adsorption capacity of iron.Existing ferropexy film is 1.6 times of the soaked rear expansions of gelling, and the Chelex-100 distribution density of fixing film sedimentation face also decreases 1.6 times, causes the adsorption capacity of iron is declined.After fixing film gelling of the present invention is soaked, do not expand, sedimentation face Chelex-100 distribution density is higher than existing ferropexy film, the therefore corresponding raising of adsorption capacity.In addition, we find that hydronium(ion) oxidation zirconium has ambisexuality, positively charged and negative electrical charge of while in the above environment of pH 5.0, and Phosphate Sorption and iron ion, impel fixing film of the present invention significantly to rise to the adsorption capacity of iron simultaneously.
3) collocation of the fixing two kinds of fixatives of film of the present invention is reasonable.Fixing film depends on the distribution of adsorbent on film surface to the absorption property of object; Distribution density is larger, and absorption property is stronger.Realize the function of two kinds of objects of the synchronous enrichment of a kind of fixing film, two kinds of adsorbents that adopt all need to form reasonably and distribute on fixing film surface, make adsorbent can produce suction-operated and have certain adsorption capacity.The fixing film of the present invention adopts respectively zirconium hydroxide and the Chelex-100 adsorbent as phosphorus and iron, wherein large (200-400 order) of Chelex-100 grain diameter, to preferentially be deposited to surface, unformed hydronium(ion) oxidation zirconium light specific gravity, sedimentation subsequently is also distributed in the remaining surface part not occupied by Chelex-100, make fixing film surface distribute zirconium hydroxide and Chelex-100, simultaneously Phosphate Sorption and iron ion simultaneously.To the optimization of hydronium(ion) oxidation zirconium and Chelex-100 addition, can make fixing film zirconium hydroxide of the present invention and Chelex-100 reasonable in the distribution density on fixing film surface, adsorption capacity is large, reaches the function of synchronous high-efficiency enriched phosphorus and iron.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with detailed description of the invention, but is limited by claim.
Brief description of the drawings
The electron-microscope scanning image (amplifying 50 times) on Fig. 1 synchronous enriched phosphorus of the present invention and ferropexy film surface, can see the distribution of fixing film surface C helex-100 particle, is around zirconium hydroxide.Before scanning, fixing film is through potassium permanganate dyeing.
The impact of the fixing film Chelex-100 resin content of Fig. 2 A the present invention on iron absorption property.In the time that Chelex-100 resin content changes to 1g from 0.6g, fixing film is to compared with the absorption property of iron and the fixing film of current commercial Chelex-100 resin, and absorption property obviously strengthens, and 120 minutes time, ferrous adsorption rate is brought up to 100% by 40%.
The impact of the fixing film Chelex-100 resin content of Fig. 2 B the present invention on phosphorus absorption property.In the time that Chelex-100 resin content changes to 1g from 0.6g, fixing film to the absorption property of phosphorus with do not add Chelex-100 resin-phase ratio and there is no notable difference.
The adsorption capacity contrast of the fixing film DGT device of the fixing film DGT device of Fig. 3 A the present invention and current commercial Chelex-100 resin to ferrous ion.The present invention fixes film ferrous iron fixed capacity 70 ± 2 μ g cm
-2, fix film to ferrous iron fixed capacity (45 ± 5 μ g cm apparently higher than commercial Chelex-100 resin
-2).
The fixing film DGT device of Fig. 3 B the present invention and the adsorption capacity contrast of the fixing film DGT device of zirconium hydroxide to phosphate radical phosphorus.The present invention is fixing, and film is 83 ± 2 μ g cm to phosphate radical phosphorus fixation capacity
-2, fix film to phosphate radical phosphorus fixation capacity (100 μ g cm than single zirconium hydroxide
-2) lower slightly, but than at least 3.5 times of the fixed capacity height of other fixing films.
Detailed description of the invention
Embodiment 1
A fixing film for synchronous enriched phosphorus and iron, its preparation method is as follows:
Regulate the zirconium oxychloride aqueous solution pH of 0.1M reach and be stabilized in 7.0 ± 0.2 with 25% ammoniacal liquor, the precipitate with deionized water producing is washed till does not have chlorion, precipitation is after centrifugal removal supernatant, dry with hair-dryer, to its moisture content be 50 ± 5%, clay into power with mortar again, obtain the hydronium(ion) oxidation zirconium powder end of moisture content 50 ± 5%.
Hydronium(ion) oxidation zirconium powder end and 5mL 30% polyacrylamide solution of 1g moisture content 50 ± 5% are mixed in mortar, grind 10min, be transferred in 10ml centrifuge tube, add 1g Chelex-100 cationic ion-exchange resin to mix and obtain film forming liquid, to the ammonium persulfate and the 8 μ L TEMED that add 16 μ L 10% (wt) in film forming liquid, after mixing fast, it is slowly injected to the space of the mould of two glass sheets compositions of the U-shaped plastic tab that accompanies 0.4mm, even thickness again; After bubble is caught up with to the greatest extent, glass plate horizontal positioned half an hour under 2-4 DEG C of low temperature, make hydronium(ion) oxidation zirconium and Chelex-100 Particle free be deposited to bottom, one side is the front of fixing film downwards; Then be warming up to 45 ± 5 DEG C, place more than half an hour, make the film forming sol film that congeals into.Then glass plate is pried open, taken out gel film, put into deionized water and soak 24 hours, change during this time water 3 times.
The microscope enlarged image of prepared fixing film and existing ferropexy film (Chelex film) and phosphorus fixing film (ZrO film) is shown in Fig. 1, its Surface Hydrogen zirconia and the densification of Chelex-100 even particle distribution.
The fixing film of the above-mentioned synchronous enriched phosphorus making and iron is cut into the disk of diameter 1.1cm, puts into and contain 0.2mg L simultaneously
-1phosphorus and ferrous solution in, under room temperature, vibrate 120 minutes, fixing film to the bioaccumulation efficiency curve of phosphorus and iron as shown in Figure 2.Fixing film all increases along with duration of oscillation the enriching quantity of phosphorus and iron, and both increase trend is very similar, and enrichment is after 120 minutes, and fixing film all reaches more than 98% the bioaccumulation efficiency of phosphorus and iron.
Embodiment 2
A fixing film for synchronous enriched phosphorus and iron, its preparation method is as follows:
Prepare the hydronium(ion) oxidation zirconium powder end of moisture content 50 ± 5% according to the method for embodiment 1.
Hydronium(ion) oxidation zirconium powder end and 5mL 30% polyacrylamide solution of 1g moisture content 50 ± 5% are mixed in mortar, grind 10min, be transferred in 10ml centrifuge tube, add 0.8g Chelex-100 cationic ion-exchange resin to mix and obtain film forming liquid, to the ammonium persulfate and the 8 μ L TEMED that add 16 μ L 10% (wt) in film forming liquid, after mixing fast, it is slowly injected to the space of the mould of two glass sheets compositions of the U-shaped plastic tab that accompanies 0.4mm, even thickness again; After bubble is caught up with to the greatest extent, glass plate horizontal positioned half an hour under 2-4 DEG C of low temperature, make hydronium(ion) oxidation zirconium and Chelex-100 Particle free be deposited to bottom, one side is the front of fixing film downwards; Then be warming up to 45 ± 5 DEG C, place more than half an hour, make the film forming sol film that congeals into.Then glass plate is pried open, taken out gel film, put into deionized water and soak 24 hours, change during this time water 3 times.
Its Surface Hydrogen zirconia of prepared fixing film and the densification of Chelex-100 even particle distribution.Fixing film to the bioaccumulation efficiency curve of phosphorus and iron as shown in Figure 2.
Embodiment 3
A fixing film for synchronous enriched phosphorus and iron, its preparation method is as follows:
Prepare the hydronium(ion) oxidation zirconium powder end of moisture content 55% according to the method for embodiment 1.
Hydronium(ion) oxidation zirconium powder end and 5mL 30% polyacrylamide solution of 1g moisture content 50 ± 5% are mixed in mortar, grind 10min, be transferred in 10ml centrifuge tube, add 0.6g Chelex-100 cationic ion-exchange resin to mix and obtain film forming liquid, to the ammonium persulfate and the 8 μ L TEMED that add 16 μ L 10% (wt) in film forming liquid, after mixing fast, it is slowly injected to the space of the mould of two glass sheets compositions of the U-shaped plastic tab that accompanies 0.4mm, even thickness again; After bubble is caught up with to the greatest extent, glass plate horizontal positioned half an hour under 2-4 DEG C of low temperature, make hydronium(ion) oxidation zirconium and Chelex-100 Particle free be deposited to bottom, one side is the front of fixing film downwards, then be warming up to 45 ± 5 DEG C, place more than half an hour, make the film forming sol film that congeals into.Then glass plate is pried open, taken out gel film, put into deionized water and soak 24 hours, change during this time water 3 times.
Its Surface Hydrogen zirconia of prepared fixing film and the densification of Chelex-100 even particle distribution.Fixing film to the bioaccumulation efficiency curve of phosphorus and iron as shown in Figure 2.
Claims (7)
1. a fixing film for synchronous enriched phosphorus and iron, is characterized in that: this fixing film is by the film forming liquid that comprises hydronium(ion) oxidation zirconium, Chelex-100 cationic ion-exchange resin and polyacrylamide, the gel film of making after gelling.
2. the fixing film of synchronous enriched phosphorus according to claim 1 and iron, is characterized in that: described fixing film surface deposition zirconium hydroxide and Chelex-100 cationic ion-exchange resin.
3. the fixing film of synchronous enriched phosphorus according to claim 1 and iron, is characterized in that: in described fixing film, the weight ratio of hydronium(ion) oxidation zirconium and Chelex-100 cationic ion-exchange resin is 1:0.6～1:1.
4. the fixing film of synchronous enriched phosphorus according to claim 1 and iron, it is characterized in that, described fixing film adopts following methods to make, by 1g hydronium(ion) oxidation zirconium powder end and 0.6～1g Chelex-100 cationic ion-exchange resin and polyacrylamide solution mixing, make uniform film forming liquid, add after appropriate tetramethyl diethylamine and ammonium persulfate, by in this film forming liquid implantation glass mould, horizontal positioned under 2-4 DEG C of low temperature, make after zirconium hydroxide and Chelex-100 free settling, be warming up to again 45 ± 5 DEG C of placements, the film until film forming sol congeals into.
5. the preparation method of the fixing film of a synchronous enriched phosphorus claimed in claim 1 and iron, it is characterized in that, described fixing film adopts following methods to make, by 1g hydronium(ion) oxidation zirconium powder end and 0.6～1g Chelex-100 cationic ion-exchange resin and polyacrylamide solution mixing, make uniform film forming liquid, add after appropriate tetramethyl diethylamine and ammonium persulfate, by in this film forming liquid implantation glass mould, horizontal positioned under 2～4 DEG C of low temperature, make after zirconium hydroxide and Chelex-100 free settling, be warming up to again 45 ± 5 DEG C of placements, the film until film forming sol congeals into.
6. the preparation method of fixing film according to claim 5, is characterized in that, described method comprises the following steps:
1) rear grinding mixed in the hydronium(ion) oxidation zirconium powder end of 1g moisture content 50 ± 5% and 3～5mL, 30% polyacrylamide solution, add 0.6～1g Chelex-100 cationic ion-exchange resin to mix and obtain film forming liquid;
2) again to the ammonium persulfate and 4～8 μ L tetramethyl diethylamine that add 12～16 μ L 10 wt % in the film forming liquid of step 1) gained, mix in the space of even thickness between two glass sheets of rear implantation glass mould, bubble is caught up with to the greatest extent;
3) glass mold more than horizontal positioned 30min, makes hydronium(ion) oxidation zirconium and Chelex-100 Particle free be deposited to bottom under 2～4 DEG C of low temperature, is then warming up to 45 ± 1 DEG C, more than placing half an hour, and the film until film forming sol congeals into;
4) take out after gel film, put into deionized water and soak more than 24 hours, make described synchronous enriched phosphorus and the fixing film of iron.
7. according to the preparation method of the fixing film described in claim 5 or 6, it is characterized in that: prepare by the following method at described hydronium(ion) oxidation zirconium powder end, with 25% ammoniacal liquor regulate 0.1M zirconium oxychloride aqueous solution to pH be 7.0 ± 0.2, the precipitate with deionized water producing is washed till without chlorion, precipitation is after centrifugation, being dried and controlling its moisture content is between 50 ± 5%, then grind into powder.
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| CN201310076971.XA CN104043409B (en) | 2013-03-12 | 2013-03-12 | A kind of fixing film synchronizing enriched phosphorus and ferrum and preparation method thereof |
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| CN108097221A (en) * | 2017-11-28 | 2018-06-01 | 农业部环境保护科研监测所 | Heavy metal and organic matter adsorption gel material, gel adsorption body and its preparation method and application |
| CN108680726A (en) * | 2018-05-08 | 2018-10-19 | 中国科学院地球化学研究所 | Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II) |
| CN108745001A (en) * | 2018-03-09 | 2018-11-06 | 南京智感环境科技有限公司 | The DGT of methyl mercury and metal mercury ion fixes film, preparation method, DGT devices and eluent in deposit |
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Granted publication date: 20160817 |