CN114715994B - PH response type nano iron-based slow release material, preparation method and application - Google Patents

PH response type nano iron-based slow release material, preparation method and application Download PDF

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CN114715994B
CN114715994B CN202210076991.6A CN202210076991A CN114715994B CN 114715994 B CN114715994 B CN 114715994B CN 202210076991 A CN202210076991 A CN 202210076991A CN 114715994 B CN114715994 B CN 114715994B
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iron
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release material
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solution
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CN114715994A (en
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张辉
丁德馨
贺桂成
刘雅岚
刘欣媛
胡南
李峰
马建洪
丁洋
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University of South China
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the technical field of uranium-polluted groundwater remediation, and discloses a pH-responsive nano iron-based slow-release material, a preparation method and application thereof, wherein the preparation method of the pH-responsive nano iron-based slow-release material comprises the following steps: preparing a nano iron-based material; preparing a cross-linked chitosan solution with pH response; the cross-linked chitosan wraps the nano iron-based material; and carrying out solid-liquid separation, washing and drying on the obtained precipitate to obtain the pH response type nano iron-based slow release material for repairing the uranium polluted underground water of the acid-process leaching mine. The nano slow-release material prepared by the invention can slowly release the nano iron-based material under the acidic condition, and the released nano iron-based material can improve the pH value of acidic uranium polluted groundwater on one hand, and fix uranium in the groundwater by adsorption and chemical reduction on the other hand. The nanometer slow-release material has the advantages of small particle size (20-100 nm), good migration and diffusion performance, long action period, stable structure, low cost, environmental friendliness and the like.

Description

PH response type nano iron-based slow release material, preparation method and application
Technical Field
The invention belongs to the technical field of uranium-polluted groundwater remediation, and particularly relates to a pH response type nano iron-based slow release material, a preparation method and application.
Background
The natural purification method is always promoted on the treatment of the underground water of the acid-process field leaching mine abroad, and the natural purification method mainly reduces the concentration of pollutants through the flowing of the natural underground water and the adsorption and precipitation of the sediments on the pollutants, and is limited by the pore structure of an ore layer and the speed of underground water flow. In addition, scholars at home and abroad also explore the method for repairing the acid process ground leaching mine groundwater by adopting a chemical precipitation method, a permeable reactive barrier technology and a pumping-out and re-treatment method, but the repairing effect is not satisfactory. Chemical reagent needs to be added in the chemical precipitation method, the price is high, and the repair range is limited; the permeable reactive barrier technology has higher repair cost and is suitable for treating shallow groundwater; the effectiveness and sustainability of the repair of the extraction-reprocessing method will gradually decrease with the increase of the repair time. In-situ reduction and in-situ mineralization of microorganisms are further proposed to repair uranium-polluted groundwater, however, researches show that microbial community in a sediment sample after long-term acid leaching has single structure and weak biological activity, sulfate reducing bacteria and Fe (III) reducing bacteria related to U (VI) reduction in the sediment are difficult to activate, and therefore, the in-situ microbial reduction method or the in-situ microbial mineralization method is adopted to repair groundwater in retired mining areas of uranium mine mountain leaching in an acid method, and ideal effects are difficult to achieve. Therefore, it is urgent to develop a more efficient and cheaper method for repairing the uranium-polluted groundwater in the acid-process leaching mine.
The nano zero-valent iron (nZVI) is a novel environment restoration material with a special core-shell structure, has the advantages of large specific surface area, low toxicity, low cost, easy preparation and the like, can remove uranium pollutants in a chemical reduction and adsorption precipitation mode, and is widely focused in the field of restoration of uranium polluted surface water and groundwater environment. However, the nZVI has the problems of easy agglomeration, easy passivation, easy loss and poor electron selectivity in water, so that the nZVI still has limitations in the aspects of in-situ restoration and storage of underground water.
Through the above analysis, the problems and defects existing in the prior art are as follows:
(1) The natural purification method mainly reduces the concentration of pollutants through the flowing of natural underground water and the adsorption and precipitation of sediments on the pollutants, and is limited by the pore structure of an ore layer and the speed of underground water flow.
(2) The restoration effect of restoring the acid-process ground-immersed mine groundwater by adopting a chemical precipitation method, a permeable reactive barrier technology and a pumping-out and re-treatment method is not satisfactory; chemical reagent needs to be added in the chemical precipitation method, the price is high, and the repair range is limited; the technology of the permeable reactive barrier has higher repair cost and is suitable for treating shallow groundwater; the effectiveness and sustainability of the repair of the extraction-reprocessing method will gradually decrease with the increase of the repair time.
(3) In the method for restoring uranium-polluted groundwater by adopting in-situ reduction and in-situ mineralization of microorganisms, the microbial community in the sediment sample after long-term acid leaching has single structure and weak biological activity, sulfate reducing bacteria and Fe reducing bacteria related to U reduction in the sediment are difficult to activate, and ideal effects are difficult to achieve.
(4) The nZVI has the problems of easy agglomeration, easy passivation, easy loss and poor electron selectivity in water, so that the nZVI still has limitations in the aspects of in-situ restoration and storage of underground water and the like.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a pH response type nano iron-based slow release material, a preparation method and application thereof, and particularly relates to a uranium-polluted groundwater repair slow release material, a preparation method thereof and application thereof in-situ repair of uranium-polluted groundwater in an acid-process leaching mine.
The invention discloses a preparation method of a pH response type nano iron-based slow release material, which comprises the following steps:
step one, preparing a nano iron-based material; wherein the nano iron-based material comprises carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron;
step two, preparing a crosslinked chitosan solution with pH response;
step three, cross-linking chitosan to wrap the nano iron-based material;
and step four, carrying out solid-liquid separation, washing and drying on the precipitate obtained in the step three to obtain the pH response type nano iron-based slow release material for repairing the uranium polluted underground water of the acid-process leaching mine.
Further, in the first step, the preparing a nano iron-based material includes:
weighing 0.01mol of iron source to dissolve in 1L of deionized waterAdding a certain amount of carboxymethyl cellulose, a sulfur source or a phosphorus source into water, introducing nitrogen, stirring for 30 min; 100mL of 0.4mol/L NaHB was added dropwise to the solution 4 Dropwise adding the solution within 10min, and continuously stirring for 2h to respectively obtain carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron solutions; and separating the carboxymethyl cellulose modified nano zero-valent iron, the vulcanized nano zero-valent iron and the phosphorylated nano zero-valent iron, respectively washing for 3 times by using oxygen-free deionized water and oxygen-free ethanol, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron powder.
Further, the iron source is ferric chloride, ferrous chloride, ferric sulfate and ferrous sulfate, preferably ferrous chloride; the sulfur source is sodium dithionite, sodium hydrosulfide and sodium sulfide, preferably sodium dithionite; the phosphorus source is potassium dihydrogen phosphate and sodium tripolyphosphate, preferably potassium dihydrogen phosphate.
The molar ratio of the carboxymethyl cellulose, the sulfur source or the phosphorus source to the iron source is 1:100-1:10, preferably 1:10.
Further, in step two, the preparing a cross-linked chitosan solution having a pH response includes:
preparing 50mL of chitosan solution with a certain concentration by adopting 1% HCl, preparing 10mL of sodium tripolyphosphate solution with a certain concentration, dripping the sodium tripolyphosphate solution into the chitosan solution at a speed of 1mL/min, and mechanically and continuously stirring for 10min at a speed of 1000rmp/min to obtain the crosslinked chitosan solution with pH response.
Further, the concentration of the chitosan solution is 0.5g/L to 10g/L, preferably 5g/L; the concentration of the sodium tripolyphosphate solution is 0.5g/L to 10g/L, preferably 5g/L.
Further, in the third step, the crosslinked chitosan encapsulates the nano iron-based material, and the method comprises the following steps:
weighing a certain amount of carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron powder, dispersing in 500mL of anaerobic deionized water, and introducing nitrogen for protection; dropwise adding the crosslinked chitosan solution in the third step at a speed of 1 mL/min; and (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
Further, the carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron powder are 0.5 g-5 g, preferably 2.5g.
In the fourth step, the obtained precipitate is subjected to solid-liquid separation, washing and drying to obtain the pH response type nano iron-based slow release material for repairing the uranium polluted underground water of the acid-process leaching mine, which comprises the following steps:
centrifugally separating the precipitate obtained in the third step by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, and after 10min of centrifugation, adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for a plurality of times until the solution is neutral after water is added; and (3) drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
The invention further aims to provide the pH response type nano iron-based slow release material prepared by the preparation method of the pH response type nano iron-based slow release material, wherein the pH response type nano iron-based slow release material is uniform in size and has particle size distribution of 20-100 nm.
The invention further aims to provide an application of the pH response type nano iron-based slow release material in repairing the uranium-polluted underground water of an acid-process leaching mine, and an application method of the pH response type nano iron-based slow release material in repairing the uranium-polluted underground water of the acid-process leaching mine comprises the following steps:
50g of core sample after acid process in-situ leaching is added into a 1L wide-mouth bottle, 1L of acid process in-situ leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, 0.1 g-5.0 g of pH response type nano iron-based slow release material is added, the uranium concentration in the acid process in-situ leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02.
By combining all the technical schemes, the invention has the advantages and positive effects that: aiming at the problems of nZVI in groundwater remediation application, the invention develops a pH response type nano iron-based slow release material and is applied to the remediation of groundwater polluted by uranium in an acid process leaching mine.
According to the invention, carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron are synthesized, so that the problems of easy agglomeration, easy passivation and easy loss of nZVI are solved, and the electron selectivity is improved; and then coating a layer of pH responsive crosslinked chitosan on the surface of the material, and controlling the slow release of the nano iron-base (carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron) in the acidic groundwater. On one hand, the nano iron-based can improve the pH value of the acid uranium polluted groundwater in the release process, and reconstruct the environment which is favorable for uranium adsorption and reduction; on the other hand, the uranium in the groundwater is fixed through adsorption and chemical reduction, so that the restoration of the uranium-polluted groundwater of the acid-process leaching mine is realized.
The nano slow-release material prepared by the invention can slowly release the nano iron-based material under the acidic condition, and the released nano iron-based material can improve the pH value of acidic uranium polluted groundwater on one hand, and fix uranium in the groundwater by adsorption and chemical reduction on the other hand. The nanometer slow-release material has the advantages of small particle size (20-100 nm), good migration and diffusion performance, long action period, stable structure, low cost, environmental friendliness and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a preparation method of a pH-responsive nano iron-based slow release material provided by an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Aiming at the problems existing in the prior art, the invention provides a pH response type nano iron-based slow release material, a preparation method and application thereof, and the invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the preparation method of the pH-responsive nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
s101, preparing a nano iron-based material;
s102, preparing a cross-linked chitosan solution with pH response;
s103, coating the nano iron-based material with crosslinked chitosan;
s104, carrying out solid-liquid separation, washing and drying on the precipitate obtained in the S103 to obtain the pH response type nano iron-based slow release material for repairing the uranium polluted underground water of the acid-process leaching mine.
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) Weighing 0.01mol of ferric chloride, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, adding 0.001mol of carboxymethyl cellulose, and then dropwise adding 100mL of 0.4mol/L NaHB into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain carboxymethyl cellulose modified nano zero-valent iron solutions respectively. And separating the carboxymethyl cellulose modified nano zero-valent iron, washing with oxygen-free deionized water and oxygen-free ethanol for 3 times respectively, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron powder.
(2) 50mL of 5.0g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 5.0g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of carboxymethyl cellulose modified nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and nitrogen is introduced for protection, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 2:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) Weighing 0.01mol of ferric sulfate, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, adding 0.0005mol of carboxymethyl cellulose, and then dropwise adding 100mL of 0.4mol/L NaHB into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain carboxymethyl cellulose modified nano zero-valent iron solutions respectively. And separating the carboxymethyl cellulose modified nano zero-valent iron, washing with oxygen-free deionized water and oxygen-free ethanol for 3 times respectively, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron powder.
(2) 50mL of 2.5g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.5g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.0g of carboxymethyl cellulose modified nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and nitrogen is introduced for protection, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 3:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) 0.01mol of ferric chloride is weighed and dissolved in 1L of deionized water, nitrogen is introduced and stirred for 30min, 0.0005mol of carboxymethyl cellulose is added, and 100mL of 0.4mol/L NaHB is then added dropwise into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain carboxymethyl cellulose modified nano zero-valent iron solutions respectively. And separating the carboxymethyl cellulose modified nano zero-valent iron, washing with oxygen-free deionized water and oxygen-free ethanol for 3 times respectively, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron powder.
(2) 50mL of 2.5g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.5g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of carboxymethyl cellulose modified nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and nitrogen is introduced for protection, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 4:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) 0.01mol of ferrous chloride is weighed and dissolved in 1L of deionized water, and then nitrogen is introduced to stirFor 30min, 0.001mol of carboxymethyl cellulose was added, and 100mL of 0.4mol/L NaHB was then added dropwise to the above solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain carboxymethyl cellulose modified nano zero-valent iron solutions respectively. And separating the carboxymethyl cellulose modified nano zero-valent iron, washing with oxygen-free deionized water and oxygen-free ethanol for 3 times respectively, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron powder.
(2) 50mL of 2.0g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.0g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of carboxymethyl cellulose modified nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and nitrogen is introduced for protection, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 5:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) Weighing 0.01mol of ferric chloride, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, adding 0.001mol of sodium dithionite, and then dropwise adding 100mL of 0.4mol/L NaHB into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain vulcanized nano zero-valent iron solutions respectively. The vulcanized nano zero-valent iron is separated, washed for 3 times by oxygen-free deionized water and oxygen-free ethanol respectively, and then blown with nitrogen for drying, so as to obtain vulcanized nano zero-valent iron powder.
(2) 50mL of 2.5g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.5g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of vulcanized nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 6:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) 0.01mol of ferric chloride is weighed and dissolved in 1L of deionized water, nitrogen is introduced and stirred for 30min, 0.0002mol of sodium sulfide is added, and 100mL of 0.4mol/L NaHB is then added dropwise into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain vulcanized nano zero-valent iron solutions respectively. The vulcanized nano zero-valent iron is separated, washed for 3 times by oxygen-free deionized water and oxygen-free ethanol respectively, and then blown with nitrogen for drying, so as to obtain vulcanized nano zero-valent iron powder.
(2) 50mL of 2.5g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.5g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of vulcanized nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 7:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) Weighing 0.01mol of ferrous chloride, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, adding 0.001mol of sodium hydrosulfide, and then dropwise adding 100mL of 0.4mol/L NaHB into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain vulcanized nano zero-valent iron solutions respectively. The vulcanized nano zero-valent iron is separated, washed for 3 times by oxygen-free deionized water and oxygen-free ethanol respectively, and then blown with nitrogen for drying, so as to obtain vulcanized nano zero-valent iron powder.
(2) 50mL of 2.0g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.0g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of vulcanized nano zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 8:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) 0.01mol of ferric chloride is weighed and dissolved in 1L of deionized water, nitrogen is introduced and stirred for 30min, 0.001mol of monopotassium phosphate is added, and 100mL of 0.4mol/L NaHB is then added dropwise into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain the phosphorylated nanometer zero-valent iron solution respectively. The phosphorylated nanometer zero-valent iron is separated, washed for 3 times by anaerobic deionized water and anaerobic ethanol respectively, and then blown with nitrogen for drying, thus obtaining phosphorylated nanometer zero-valent iron powder.
(2) 50mL of 2.5g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 2.5g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 2.5g of phosphorylated nanometer zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 9:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) Weighing 0.01mol of ferrous chloride, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, adding 0.001mol of potassium dihydrogen phosphate, and then dropwise adding 100mL of 0.4mol/L NaHB into the solution 4 Solution, 10miAnd (3) after the dripping in the n, continuously stirring for 2 hours to respectively obtain the phosphorylated nanometer zero-valent iron solution. The phosphorylated nanometer zero-valent iron is separated, washed for 3 times by anaerobic deionized water and anaerobic ethanol respectively, and then blown with nitrogen for drying, thus obtaining phosphorylated nanometer zero-valent iron powder.
(2) 50mL of 3.0g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 3.0g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 3.0g of phosphorylated nanometer zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 10:
the preparation method of the pH response type nano iron-based slow release material provided by the embodiment of the invention comprises the following steps:
(1) 0.01mol of ferric chloride is weighed and dissolved in 1L of deionized water, nitrogen is introduced and stirred for 30min, 0.001mol of sodium tripolyphosphate is added, and 100mL of 0.4mol/L NaHB is then added dropwise into the solution 4 And (3) dropwise adding the solution within 10min, and continuously stirring for 2h to obtain the phosphorylated nanometer zero-valent iron solution respectively. The phosphorylated nanometer zero-valent iron is separated, washed for 3 times by anaerobic deionized water and anaerobic ethanol respectively, and then blown with nitrogen for drying, thus obtaining phosphorylated nanometer zero-valent iron powder.
(2) 50mL of 8.0g/L chitosan solution is prepared by adopting 1% HCl, 10mL of 8.0g/L sodium tripolyphosphate solution is prepared, the sodium tripolyphosphate solution is dropwise added into the chitosan solution at the speed of 1mL/min, and the solution is mechanically and continuously stirred for 10min at the speed of 1000rmp/min, so that the crosslinked chitosan solution with pH response is obtained.
(3) 5.0g of phosphorylated nanometer zero-valent iron powder is weighed, dispersed in 500mL of oxygen-free deionized water, and is protected by nitrogen, and then the crosslinked chitosan solution in the step (2) is dripped at a speed of 1 mL/min. And (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
(4) And (3) centrifugally separating the precipitate obtained in the step (3) by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, centrifuging for 10min, and then adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for several times until the solution is neutral after water is added. And drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
Example 11:
50g of core sample subjected to acid process on-site leaching is added into a 1L wide-mouth bottle, 1L of acid process on-site leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, then 1.0g of pH response type nano iron-based slow release material in the embodiment 1 is added, the uranium concentration in the acid process on-site leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02. After 30min of reaction, the pH of the groundwater and the concentration of uranium are measured, and the result shows that the pH of the groundwater rises to 5.08, and the removal rate of uranium reaches 94.8%.
Example 12:
50g of core sample subjected to acid process on-site leaching is added into a 1L wide-mouth bottle, 1L of acid process on-site leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, then 0.5g of pH response type nano iron-based slow release material in example 5 is added, the uranium concentration in the acid process on-site leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02. After 30min of reaction, the pH of the groundwater and the concentration of uranium are measured, and the result shows that the pH of the groundwater rises to 4.11, and the removal rate of uranium reaches 90.5%.
Example 13:
50g of core sample subjected to acid process on-site leaching is added into a 1L wide-mouth bottle, 1L of acid process on-site leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, then 2.0g of pH response type nano iron-based slow release material in example 5 is added, the uranium concentration in the acid process on-site leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02. After 30min of reaction, the pH of the groundwater and the concentration of uranium are measured, and the result shows that the pH of the groundwater rises to 5.38, and the removal rate of uranium reaches 98.2%.
Example 14:
50g of core sample subjected to acid process on-site leaching is added into a 1L wide-mouth bottle, 1L of acid process on-site leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, then 1.0g of pH response type nano iron-based slow release material in example 8 is added, the uranium concentration in the acid process on-site leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02. After 30min of reaction, the pH of the groundwater and the concentration of uranium are measured, and the result shows that the pH of the groundwater is raised to 5.05, and the removal rate of uranium is 96.3%.
Example 15:
50g of core sample subjected to acid process on-site leaching is added into a 1L wide-mouth bottle, 1L of acid process on-site leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, then 3.0g of pH response type nano iron-based slow release material in example 8 is added, the uranium concentration in the acid process on-site leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02. After 30min of reaction, the pH of the groundwater and the concentration of uranium are measured, and the result shows that the pH of the groundwater rises to 5.86, and the removal rate of uranium reaches 99.3%.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (8)

1. The preparation method of the pH response type nano iron-based slow release material is characterized by comprising the following steps of:
step one, preparing a nano iron-based material; the nano iron-based material comprises carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron or phosphorylated nano zero-valent iron;
step two, preparing a crosslinked chitosan solution with pH response; preparing 50mL of chitosan solution with a certain concentration by adopting 1% HCl, preparing 10mL of sodium tripolyphosphate solution, dripping the sodium tripolyphosphate solution into the chitosan solution at a speed of 1mL/min, and mechanically and continuously stirring for 10min at 1000rmp/min to obtain a crosslinked chitosan solution with pH response;
step three, cross-linking chitosan to wrap the nano iron-based material;
step four, carrying out solid-liquid separation, washing and drying on the precipitate obtained in the step three to obtain the pH response type nano iron-based slow release material for repairing the uranium polluted underground water of the acid-process leaching mine;
the preparing of the nano iron-based material in the first step comprises the following steps: weighing 0.01mol of iron source, dissolving in 1L of deionized water, introducing nitrogen, stirring for 30min, and adding carboxymethyl cellulose, sulfur source or phosphorus source; 100mL of 0.4mol/L NaHB was added dropwise to the solution 4 Dropwise adding the solution within 10min, and continuously stirring for 2h to respectively obtain carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron solutions; and separating the carboxymethyl cellulose modified nano zero-valent iron, the vulcanized nano zero-valent iron and the phosphorylated nano zero-valent iron, respectively washing for 3 times by using oxygen-free deionized water and oxygen-free ethanol, and then introducing nitrogen for drying to obtain carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron and phosphorylated nano zero-valent iron powder.
2. The method for preparing a pH-responsive nano-iron-based slow release material according to claim 1, wherein the iron source is ferric chloride, ferrous chloride, ferric sulfate or ferrous sulfate; the sulfur source is sodium dithionite, sodium hydrosulfide or sodium sulfide; the phosphorus source is potassium dihydrogen phosphate or sodium tripolyphosphate;
the molar ratio of the carboxymethyl cellulose, the sulfur source or the phosphorus source to the iron source is 1:100-1:10.
3. The method for preparing a pH-responsive nano iron-based slow release material according to claim 1, wherein the concentration of the chitosan solution is 0.5g/L to 10g/L; the concentration of the sodium tripolyphosphate solution is 0.5 g/L-10 g/L.
4. The method for preparing a pH-responsive nano iron-based slow release material according to claim 1, wherein the cross-linking chitosan-coated nano iron-based material in the third step comprises: weighing carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron or phosphorylated nano zero-valent iron powder, dispersing in 500mL anaerobic deionized water, and introducing nitrogen for protection; dropwise adding the crosslinked chitosan solution in the third step at a speed of 1 mL/min; and (3) mechanically and continuously stirring for 4 hours at 1000rmp/min to obtain the chitosan-coated nano iron-based material solution.
5. The method for preparing a pH-responsive nano iron-based slow release material according to claim 4, wherein the carboxymethyl cellulose modified nano zero-valent iron, vulcanized nano zero-valent iron or phosphorylated nano zero-valent iron powder is 0.5 g-5 g.
6. The method for preparing the pH-responsive nano iron-based slow release material according to claim 1, wherein the step four of performing solid-liquid separation, washing and drying on the obtained precipitate to obtain the pH-responsive nano iron-based slow release material for repairing uranium-contaminated groundwater of an acid-process leaching mine comprises: centrifugally separating the precipitate obtained in the third step by adopting a high-speed centrifugal machine, wherein the centrifugal speed is 15000rmp/min, and after 10min of centrifugation, adding 50mL of anaerobic deionized water or anaerobic ethanol for washing for a plurality of times until the solution is neutral after water is added; and (3) drying the precipitate by adopting nitrogen, and grinding until no granular feel exists, thereby obtaining the pH response type nano iron-based slow release material for repairing the uranium-polluted underground water of the acid-process leaching mine.
7. A pH-responsive nano-iron-based slow release material prepared by the method for preparing a pH-responsive nano-iron-based slow release material according to any one of claims 1 to 6, characterized in that the pH-responsive nano-iron-based slow release material has a uniform size and a particle size distribution of 20nm to 100nm.
8. The application of the pH-responsive nano iron-based slow release material in the restoration of uranium-polluted underground water of an acid-process leaching mine according to claim 7, wherein the application method of the pH-responsive nano iron-based slow release material in the restoration of uranium-polluted underground water of the acid-process leaching mine comprises the following steps: 50g of core sample after acid process in-situ leaching is added into a 1L wide-mouth bottle, 1L of acid process in-situ leaching mine uranium polluted groundwater is added, nitrogen is introduced for 1h, 0.1 g-5.0 g of pH response type nano iron-based slow release material is added, the uranium concentration in the acid process in-situ leaching mine uranium polluted groundwater is 1.15mg/L, and the pH of the groundwater is 3.02.
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