CN105771936A - Magnetic zirconium/iron composite oxide nanometer material, and preparation method and application thereof - Google Patents
Magnetic zirconium/iron composite oxide nanometer material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic zirconium/iron composite oxide nanometer material, and a preparation method and application thereof. The magnetic zirconium/iron composite oxide nanometer material is prepared by using FeSO4, Fe2(SO4)3 and ZrOCl2 as raw materials through NaOH coprecipitation and hydrothermal curing. The preparation method is characterized in that NaOH is dripped into a mixed solution containing the FeSO4, the Fe2(SO4)3 and the ZrOCl2 for performing co-precipitation reaction to obtain serous fluid; the serous fluid is subjected to hydrothermal curing treatment to obtain magnetic serous fluid; the magnetic serous fluid is cleaned and dried to obtain the magnetic zirconium/iron composite oxide nanometer material. The magnetic zirconium/iron composite oxide nanometer material has the advantages that the ingredients are simple; secondary pollution caused by dissolving harmful ions into water is avoided; the magnetic zirconium/iron composite oxide nanometer material can be used for treating phosphorus-containing wastewater; the phosphorus adsorption capacity is great; the adsorption effect is obvious.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of magnetic zirconium/iron compound oxide nano material and its preparation method and application.
Background technology
Along with the fast development of industrialization and urbanization, P elements content in the environment is gradually increased.Showing according to " China Environmental State Bulletin in 2014 ", fresh water environment aspect, total phosphorus is one of the main contamination index in whole nation trunk river and lake；Ocean water environment aspect, reactive phosphate is one of the main contamination index at the East Sea and the South Sea.A large amount of scientific researches are it has been verified that nitrogen and phosphorus can promote hydrobiological growth, and finally cause body eutrophication, and phosphorus is considered as the main factor producing body eutrophication.Water ecological setting and fishery cultivating all can be produced harm greatly by eutrophication water, additionally, some algae in eutrophication water releasably goes out extremely toxic substance, it is possible to be detrimental to health by food chain.
The body eutrophication case frequency caused due to mankind's activity appears in the newspapers end, thus the water body dephosphorized attention being also increasingly subject to researcher.Current dephosphorization mainly has the sedimentation method, bioanalysis, absorption method etc..Absorption method is owing to technique is simple, with low cost and high treating effect and the concern of extremely people.The selection of adsorbent is the key of absorption method dephosphorization.The adsorbent that flyash, changed red mud etc. are cheap, although their high treating effect, but due to the complicated component of these adsorbing materials own, while removing phosphorus, generally have harmful ion dissolve in water, cause secondary pollution；Some such as adsorbents such as activated carbon, zirconium oxide are widely used because it has bigger specific surface and more adsorption site, but its shortcoming be in that adsorption treatment after adsorbent be difficult to separate and recover, or reclaim cumbersome；Also have some magnetic adsorptive materials, for instance magnetic iron ore (Fe3O4Although) easily separated when externally-applied magnetic field, but it is little to the adsorption capacity of phosphorus, and the requirement in use procedure is relatively larger.How to prepare stable, easily separated and be the emphasis studied at present to the adsorbing material that the adsorption capacity of phosphorus is big.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of stable, easily separated and the adsorption capacity of phosphorus is big magnetic zirconium/iron compound oxide nano material；It addition, also provide for that a kind of synthetic method is simple, low cost, preparation method without special installation, the magnetic zirconium/iron compound oxide nano material being easy to large-scale production, can be applicable to remove the phosphorus in waste water.
For solving above-mentioned technical problem, it is provided that a kind of magnetic zirconium/iron compound oxide nano material, described magnetic zirconium/iron compound oxide nano material is with FeSO4、Fe2(SO4)3And ZrOCl2For raw material, by NaOH co-precipitation, Hydrothermal Aging prepare.
Conceive as a total technology, the preparation method that present invention also offers a kind of magnetic zirconium/iron compound oxide nano material, comprise the following steps:
S1, containing FeSO4、Fe2(SO4)3And ZrOCl2Mixed solution and dripping NaOH carry out coprecipitation reaction and obtain serosity；
S2, the described serosity in step S1 is carried out Hydrothermal Aging process, obtain magnetic serosity；
S3, the described magnetic serosity in step S2 is cleaned, dry obtain magnetic zirconium/iron compound oxide nano material.
Above-mentioned preparation method, it is preferred that described step S1 specifically includes following steps:
S1-1, by FeSO4、Fe2(SO4)3And ZrOCl2It is mixed to get mixed solution；
S1-2, NaOH solution being added drop-wise in described mixed solution, the pH value regulating described mixed solution is 10.7～11.3, carries out coprecipitation reaction and obtains coprecipitated product；
S1-3, stir described coprecipitated product and obtain serosity.
Above-mentioned preparation method, it is preferred that the drop rate of NaOH solution described in described S1-2 be 15 droplet/minute～20 droplet/minute, the concentration of described NaOH solution is 5mol/L～7mol/L；Described in described S1-3, the rotating speed of stirring is 2000rpm～2500rpm, and mixing time is 5min～10min.
Above-mentioned preparation method, preferably, in described mixed solution, the mol ratio of Fe (II): Fe (III): Zr (IV) is 4: 8: 1～6, and the total concentration of metal ions in described mixed solution is 0.756mol/L～1.125mol/L.
Above-mentioned preparation method, it is preferred that the temperature of Hydrothermal Aging process described in described S2 is 90 DEG C～95 DEG C, and the time is 18h～24h.
Above-mentioned preparation method, it is preferred that described step S3 specifically includes following steps:
S3-1, magnetic serosity is carried out solid-liquid separation, and use ultra-pure water to clean magnetic retention；
S3-2, by step S3-1 clean after magnetic retention be dried process；
S3-3, use ball mill are by the magnetic material grind into powder after drying process in step S3-2.
Above-mentioned preparation method, it is preferred that in described step S3-1, the method for described solid-liquid separation is the magnetic separation of externally-applied magnetic field.
Above-mentioned preparation method, it is preferred that in described step S3-1, described use ultra-pure water cleans and uses 1L～1.5L ultra-pure water to clean for every 10 grams of magnetic retentions, wash cycles 3 times～5 times.
Above-mentioned preparation method, it is preferred that in described step S3-2, the temperature of described dried is 90 DEG C～95 DEG C, and the time is 8h～10h.
Conceive as total technology, present invention also offers a kind of described magnetic zirconium/iron compound oxide nano material or magnetic zirconium/iron compound oxide nano material that described preparation method prepares is in the application removing Phosphorus From Wastewater.
Above-mentioned application, it is preferred that described application process is: magnetic zirconium/iron compound oxide nano material is joined in phosphorus-containing wastewater with the addition of 1.0g/L～2.0g/L, vibration absorption.
Above-mentioned application, it is preferred that the pH value of described phosphorus-containing wastewater is 2.0～8.0, phosphorus concentration is 5mg/L～100mg/L.
Above-mentioned application, it is preferred that the temperature of described vibration absorption is 25 DEG C～40 DEG C, rotating speed is 200rpm, duration of oscillation is 24h.
Compared with prior art, it is an advantage of the current invention that:
(1) the invention provides a kind of magnetic zirconium/iron compound oxide nano material, it is mainly composed of Fe3O4、γ-Fe2O3And ZrO2, its surface has a substantial amounts of oh group, and the oh group generation ion of phosphate and material surface exchanges, thus reaching to remove the purpose of Phosphorus From Wastewater.Two kinds of exchanged forms are:
Zr-OH+H2PO4 ?=Zr (H2PO4)+OH?；
2Zr-OH+HPO4 2=Zr2(H2PO4)+2OH?。
Compared in prior art such as the adsorbent such as flyash, red mud, its composition is simple, does not have harmful ion and dissolves in and cause secondary pollution in water.
(2) the magnetic zirconium/iron compound oxide nano material of the present invention has excellent magnetic, can be used for Removal of Phosphorus in Wastewater, and the adsorption capacity of phosphorus is big, and adsorption effect is obvious, compared to existing non-magnetic material, is easily achieved solid-liquid separation in utilization process.
(3) preparation method that the invention provides a kind of magnetic zirconium/iron compound oxide nano material, synthetic method for existing magnetic material is excessively loaded down with trivial details, and add pressure in a kettle. and carry out, and sintering temperature is higher in preparation process, the shortcoming that energy consumption is bigger, the present invention is with NaOH, FeSO4·7H2O、Fe2(SO4)3And ZrOCl2·8H2O is raw material, prepares black serosity by the method for co-precipitation, black serosity by after Hydrothermal Aging again cleaning-drying obtain magnetic zirconium/iron compound oxide nano material.In whole preparation process, operating procedure is simple, it is not necessary to large-scale and complicated device, and Hydrothermal Aging temperature is low；Have that technique is simple, apparatus for preparation is simple and easy, preparation cost is low and the advantage such as the cycle is short.
(4) present invention also offers a kind of magnetic zirconium/iron compound oxide applications to nanostructures.For Removal of Phosphorus in Wastewater, the magnetic zirconium/iron compound oxide nano material of the present invention can not only phosphorus in active adsorption waste water, and quick solid-liquid separation can be realized after processing procedure terminates when externally-applied magnetic field.The magnetic material little compared to other adsorption capacities and the big non-magnetic material of adsorption capacity, the magnetic zirconium/iron compound oxide nano material of the present invention has can effectively remove the advantage that phosphorus is prone to again solid-liquid separation.
Accompanying drawing explanation
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete description.
Fig. 1 is the preparation flow figure of magnetic zirconium/iron compound oxide nano material in the embodiment of the present invention 1.
Fig. 2 is scanning electron microscope (SEM) image of the magnetic zirconium/iron compound oxide nano material of preparation in the embodiment of the present invention 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the magnetic zirconium/iron compound oxide nano material of preparation in the embodiment of the present invention 1.
Fig. 4 is transmission electron microscope (TEM) image of the magnetic zirconium/iron compound oxide nano material of preparation in the embodiment of the present invention 1.
Fig. 5 is nitrogen adsorption desorption curve and the pore size distribution curve of the magnetic zirconium/iron compound oxide nano material of preparation in the embodiment of the present invention 1.
Fig. 6 is the hysteresis curve of the magnetic zirconium/iron compound oxide nano material of preparation in the embodiment of the present invention 1.
Fig. 7 be in the embodiment of the present invention 2 magnetic zirconium/iron compound oxide nano material to the adsorbance of phosphorus with adsorption time variation relation figure.
Fig. 8 is magnetic zirconium/iron compound oxide nano material clearance graph of a relation to phosphorus when different counter anion in the embodiment of the present invention 2.
Fig. 9 be in the embodiment of the present invention 3 magnetic zirconium/iron compound oxide nano material to the adsorbance of phosphorus with adsorption time variation relation figure.
Figure 10 be in the embodiment of the present invention 4 magnetic zirconium/iron compound oxide nano material to the adsorbance of phosphorus with adsorption time variation relation figure.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment
The material adopted in following example and instrument are commercially available.
Embodiment 1:
Magnetic zirconium/iron compound oxide the nano material of a kind of present invention, this magnetic zirconium/iron compound oxide nano material is with FeSO4·7H2O、Fe2(SO4)3And ZrOCl2·8H2O is raw material, by NaOH co-precipitation, Hydrothermal Aging prepares.
A kind of preparation method of above-mentioned magnetic zirconium/iron compound oxide nano material, as it is shown in figure 1, comprise the following steps:
(1) 6.95gFeSO is taken respectively4·7H2O、10.00gFe2(SO4)3And 8.05gZrOCl2·8H2O, is dissolved in 200mL deionized water, obtains mixed solution A, and with molar ratio computing Fe (II): Fe (III) of ion in this mixed solution A: Zr (IV)=4: 8: 4, total concentration of metal ions is 1.000mol/L.
(2) take 12.00g sodium hydroxide to be dissolved in 100mL deionized water, obtain the NaOH solution of 6mol/L.
(3) mixed solution A in step (1) is transferred to the there-necked flask of 1000mL and uses magnetic stirring apparatus to stir mixed liquor with the rotating speed of 2500rpm, drip the NaOH solution in (2) with in backward mixed solution with the speed of 15 droplets/minute, be stop obtaining coprecipitated product after 11 to the pH of mixed liquor.
(4) continue the coprecipitated product 5min obtained in whipping step (3), obtain the serosity of black.
(5) the black serosity obtained in step (4) is placed in baking oven and carries out Hydrothermal Aging process, curing temperature is 90 DEG C (curing temperature is 90 DEG C～95 DEG C all can be implemented), curing time controls, 18h (18h～24h all can implement), to obtain black magnetic serosity.
(6) the black magnetic serosity in step (5) is carried out Magnetic Isolation by externally-applied magnetic field, thoroughly cleaning black precipitate after Magnetic Isolation 3 times with ultra-pure water, every 10 grams of black precipitates use 1.5L ultra-pure water to clean (ultra-pure water volume is that 1～1.5L all can implement).
(7) black precipitate after cleaning being placed in baking oven inner drying, baking temperature is 90 DEG C (baking temperature is 90 DEG C～95 DEG C all can be implemented), controls drying time 8h (8h～10h all can implement).
(8) use ball mill to be pulverized by material last dried black precipitate, be placed in drying basin and preserve.
Scanning electron microscope (SEM) image of magnetic zirconium/iron compound oxide nano material prepared by the present embodiment, as shown in Figure 2.
The XRD spectra of magnetic zirconium/iron compound oxide nano material prepared by the present embodiment, as shown in Figure 3.What can analyze magnetic zirconium/iron compound oxide nano material from Fig. 3 is mainly composed of Fe3O4、γ-Fe2O3And ZrO2。
Transmission electron microscope (TEM) image of magnetic zirconium/iron compound oxide nano material prepared by the present embodiment, as shown in Figure 4.
The nitrogen adsorption desorption curve of magnetic zirconium/iron compound oxide nano material prepared by the present embodiment and pore size distribution curve, as shown in Figure 5.Magnetic zirconium/iron compound oxide the nanometer material structure prepared as can see from Figure 5 is very stable, and aperture is less, is 213.50m by the BET specific surface area tested2/g。
The hysteresis curve image of magnetic zirconium/iron compound oxide nano material prepared by the present embodiment, as shown in Figure 6.The intensity of magnetization of the magnetic zirconium/iron compound oxide nano material prepared as can see from Figure 6 is 44.9emu/g.
Embodiment 2:
The magnetic zirconium of a kind of present invention/iron compound oxide nano material application in Removal of Phosphorus in Wastewater, comprises the following steps:
(1) taking the zirconium of the magnetic in 0.1g embodiment 1/iron compound oxide nano material to join in the phosphorus-containing wastewater that 50mL initial concentration is 50mg/L and (arrange 12 Duplicate Samples according to same standard), then using the pH value that the sodium hydroxide solution of 0.1mol/L and the hydrochloric acid solution of 0.1mol/L regulate phosphorus-containing wastewater is 2.5 ± 0.2.
(2) phosphorus-containing wastewater in (1) is placed on the shaking table that temperature is 25 DEG C, sway with the speed of shaking of 200rpm, then externally-applied magnetic field is utilized to be separated by the magnetic material of differential responses time, take supernatant, the phosphorus concentration in supernatant is measured by ultraviolet-visible spectrophotometer, following equation (1) is adopted to calculate adsorbance (the i.e. unit mass magnetic zirconium/iron compound oxide nano material adsorption capacity to phosphorus of magnetic material, unit: mg/g), to judge the disposal ability to phosphorus of the adsorbent synthesized by the present invention.
In formula (1): the adsorbance (unit: mg/g) of Q magnetic material；
C0For processing the initial concentration (unit: mg/L) of phosphorus in front phosphorus-containing wastewater；
C is the concentration (unit: mg/L) of phosphorus in phosphorus-containing wastewater supernatant after processing；
M is the quality (unit: g) of adsorbent.
The amount that Fig. 7 is magnetic zirconium/iron compound oxide nano material Phosphate Sorption changes over graph of a relation.As can be seen from Figure 7, when absorption tends to balance, magnetic zirconium/iron compound oxide nano material is to the adsorbance of phosphorus up to 16.69mg/g, and this illustrates that phosphorus is had bigger adsorption capacity by the magnetic zirconium/iron compound oxide nano material of the present invention, it is possible to effectively remove the phosphorus in waste water.
(3) investigation that adsorption capacities of materials is affected by counter anion
A, the magnetic zirconium/iron compound oxide nano material taken in 0.1g embodiment 1 respectively join in the phosphorus-containing wastewater that initial phosphorus concentration is 30mg/L, the concentration of the chloride ion (preparing with NaCl in experiment) coexisted is respectively set to 0,15,30,50,100,150mgL-1, the sulfate ion coexisted (uses Na in experiment2SO4Preparation) concentration be respectively set to 0,15,30,50,100,150mgL-1, the nitrate ion coexisted (uses NaNO in experiment3Preparation) concentration be respectively set to 0,15,30,50,100,150mgL-1。
B, the phosphorus-containing wastewater in step a is placed on the shaking table that temperature is 25 DEG C, sways 24h with the speed of shaking of 200rpm, then utilize externally-applied magnetic field to be separated by magnetic material, take supernatant, measure the phosphorus concentration in supernatant by ultraviolet-visible spectrophotometer.
The clearance graph of a relation that Fig. 8 is magnetic zirconium/iron compound oxide nano material when different counter anion to phosphorus.As can be seen from Figure 8, magnetic zirconium/iron compound oxide nano material is removed phosphorus and be there is no generation impact by chloride ion, sulfate ion and the nitrate ion coexisted.This shows that the magnetic zirconium/iron compound oxide nano material of the present invention can be widely applied to process the phosphorus-containing wastewater under chloride ion, sulfate ion and nitrate ion exist.
Embodiment 3:
A kind of preparation method of the magnetic zirconium/iron compound oxide nano material of the present invention, substantially the same manner as Example 1, it is a difference in that in the present embodiment mixed solution A with molar ratio computing Fe (II): Fe (III) of ion: Zr (IV)=2: 4: 3.Magnetic zirconium/iron compound oxide the Application of micron prepared by the present embodiment is in Removal of Phosphorus in Wastewater, and application process is identical with embodiment 2.
The amount that Fig. 9 is magnetic zirconium/iron compound oxide nano material Phosphate Sorption prepared by the present embodiment changes over graph of a relation.As can be seen from Figure 9, when absorption tends to balance, magnetic zirconium/iron compound oxide nano material is to the adsorbance of phosphorus up to 17.25mg/g, and this illustrates that phosphorus is also had bigger adsorption capacity by the magnetic zirconium/iron compound oxide nano material of the present invention, it is possible to effectively remove the phosphorus in waste water.
Embodiment 4:
A kind of preparation method of the magnetic zirconium/iron compound oxide nano material of the present invention, substantially the same manner as Example 1, it is a difference in that in the present embodiment mixed solution A with molar ratio computing Fe (II): Fe (III) of ion: Zr (IV)=2: 4: 1.Magnetic zirconium/iron compound oxide the Application of micron prepared by the present embodiment is in Removal of Phosphorus in Wastewater, and application process is identical with embodiment 2.
The amount that Figure 10 is magnetic zirconium/iron compound oxide nano material Phosphate Sorption prepared by the present embodiment changes over graph of a relation.As can be seen from Figure 10, when absorption tends to balance, magnetic zirconium/iron compound oxide nano material is to the adsorbance of phosphorus up to 13.31mg/g, and this illustrates that phosphorus is also had bigger adsorption capacity by the magnetic zirconium/iron compound oxide nano material of the present invention, it is possible to effectively remove the phosphorus in waste water.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction.Although the present invention discloses as above with preferred embodiment, but is not limited to the present invention.Any those of ordinary skill in the art, when without departing from the spirit of the present invention and technical scheme, all may utilize the method for the disclosure above and technology contents and technical solution of the present invention is made many possible variations and modification, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content without departing from technical solution of the present invention, to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modify according to the technical spirit of the present invention, all still fall within the scope of technical solution of the present invention protection.
Claims (10)
1. magnetic zirconium/iron compound oxide nano material, it is characterised in that described magnetic zirconium/iron compound oxide nano material is with FeSO4、Fe2(SO4)3And ZrOCl2For raw material, by NaOH co-precipitation, Hydrothermal Aging prepare.
2. the preparation method of magnetic zirconium/iron compound oxide nano material, it is characterised in that comprise the following steps:
S1, containing FeSO4、Fe2(SO4)3And ZrOCl2Mixed solution and dripping NaOH carry out coprecipitation reaction and obtain serosity；
S2, the described serosity in step S1 is carried out Hydrothermal Aging process, obtain magnetic serosity；
S3, the described magnetic serosity in step S2 is cleaned, dry obtain magnetic zirconium/iron compound oxide nano material.
3. preparation method according to claim 2, it is characterised in that described step S1 specifically includes following steps:
S1-1, by FeSO4、Fe2(SO4)3And ZrOCl2It is mixed to get mixed solution；
S1-2, NaOH solution being added drop-wise in described mixed solution, the pH value regulating described mixed solution is 10.7～11.3, carries out coprecipitation reaction and obtains coprecipitated product；
S1-3, stir described coprecipitated product and obtain serosity.
4. preparation method according to claim 3, it is characterised in that the drop rate of NaOH solution described in described S1-2 be 15 droplet/minute～20 droplet/minute, the concentration of described NaOH solution is 5mol/L～7mol/L；Described in described S1-3, the rotating speed of stirring is 2000rpm～2500rpm, and mixing time is 5min～10min.
5. preparation method according to claim 2, it is characterized in that, in described mixed solution, the mol ratio of Fe (II): Fe (III): Zr (IV) is 4: 8: 1～6, and the total concentration of metal ions in described mixed solution is 0.756mol/L～1.125mol/L.
6. the preparation method according to any one of claim 2 to 5, it is characterised in that the temperature of Hydrothermal Aging process described in described S2 is 90 DEG C～95 DEG C, and the time is 18h～24h.
7. the preparation method according to any one of claim 2 to 5, it is characterised in that described step S3 specifically includes following steps:
S3-1, magnetic serosity is carried out solid-liquid separation, and use ultra-pure water to clean magnetic retention；
S3-2, by step S3-1 clean after magnetic retention be dried process；
S3-3, use ball mill are by the magnetic material grind into powder after drying process in step S3-2.
8. preparation method according to claim 7, it is characterised in that in described step S3-1, the method for described solid-liquid separation is the magnetic separation of externally-applied magnetic field；Described use ultra-pure water cleans and uses 1L～1.5L ultra-pure water to clean for every 10 grams of magnetic retentions, wash cycles 3 times～5 times；In described step S3-2, the temperature of described dried is 90 DEG C～95 DEG C, and the time is 8h～10h.
9. magnetic zirconium/iron compound oxide nano material that magnetic zirconium/iron compound oxide nano material described in a claim 1 or preparation method according to any one of claim 2 to 8 prepare is in the application removing Phosphorus From Wastewater, it is characterized in that, described application process is: join in phosphorus-containing wastewater by magnetic zirconium/iron compound oxide nano material with the addition of 1.0g/L～2.0g/L, vibration absorption.
10. application according to claim 9, it is characterised in that the pH value of described phosphorus-containing wastewater is 2.0～8.0, phosphorus concentration is 5mg/L～100mg/L；The temperature of described vibration absorption is 25 DEG C～40 DEG C, rotating speed is 200rpm, duration of oscillation is 24h.
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| CN109731548A (en) * | 2019-02-23 | 2019-05-10 | 华南理工大学 | A kind of active carbon/zirconium-manganese oxide composite material and the preparation method and application thereof |
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| CN109867364B (en) * | 2019-03-08 | 2021-10-08 | 上海海洋大学 | In-situ combined control system and method for releasing endogenous pollutants in aquaculture water body |
| CN111470604A (en) * | 2020-04-29 | 2020-07-31 | 中国科学院合肥物质科学研究院 | Magnetic porous iron-zirconium bimetal composite coagulant aid and preparation method and application thereof |
| CN111470604B (en) * | 2020-04-29 | 2022-04-08 | 中国科学院合肥物质科学研究院 | Magnetic porous iron-zirconium bimetal composite coagulant aid and preparation method and application thereof |
| CN113731363A (en) * | 2021-09-16 | 2021-12-03 | 河北科技大学 | Adsorbent and preparation method and application thereof |
| CN115518611A (en) * | 2022-10-17 | 2022-12-27 | 北京中岩大地环境科技有限公司 | Preparation method and application of magnetic ferrozirconium modified sepiolite artificial wetland matrix |
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| CN115722200B (en) * | 2022-11-08 | 2024-04-09 | 中国科学院上海高等研究院 | Yttrium-zirconium-based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
| CN115739003A (en) * | 2022-12-06 | 2023-03-07 | 华南理工大学 | Preparation and application of granular iron-zirconium oxide phosphorus removal adsorbent |
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