CN114832769A - Oxalate modified nano zero-valent iron material and preparation method and application thereof - Google Patents
Oxalate modified nano zero-valent iron material and preparation method and application thereof Download PDFInfo
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- CN114832769A CN114832769A CN202210506000.3A CN202210506000A CN114832769A CN 114832769 A CN114832769 A CN 114832769A CN 202210506000 A CN202210506000 A CN 202210506000A CN 114832769 A CN114832769 A CN 114832769A
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- oxalate
- valent iron
- iron material
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 27
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims abstract description 5
- 230000003993 interaction Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
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- 230000000694 effects Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
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- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
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- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 9
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- 238000011160 research Methods 0.000 description 4
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- 241000282414 Homo sapiens Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
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- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
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- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an oxalate modified nano zero-valent iron material and a preparation method and application thereof, belonging to the technical field of material and environment intersection. The oxalate modified nano zero-valent iron material is prepared by sequentially mixing ferric trichloride hexahydrate, sodium borohydride and potassium oxalate and utilizing a one-step liquid phase reduction reaction method, controlling a proper molar ratio of Ox/Fe and increasing electronegative ions and active sites on the surface of nano zero-valent iron; the carboxyl functional group of the oxalate is connected with the nano zero-valent iron in a substituted manner, so that the structural stability and the interface interaction of the modified nano material are enhanced. The preparation method of the oxalate modified nano zero-valent iron material has the characteristics of simplicity and convenience in operation, low raw material cost and environmental friendliness, and the material can be applied to treatment of lead-containing wastewater, can realize efficient parallel of three processes of lead ion reduction, adsorption and coprecipitation, and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material and environment intersection, and particularly relates to an oxalate modified nano zero-valent iron material as well as a preparation method and application thereof.
Background
Along with the rapid promotion of a series of industrial and agricultural chemicals such as mining, smelting, lead-containing waste materials, pesticides and the like, a large amount of heavy metals enter the environment in different ways, so that the problem of heavy metal pollution of soil and underground water is increasingly prominent, and the quality of agricultural products, the safety of ecological environment, the health of human beings and the sustainable development of society are seriously threatened. Lead is a typical heavy metal element widely distributed in the nature, has concealment, high toxicity, bioaccumulation and nondegradation, is one of the priority pollutants controlled by the united states environmental protection agency, and is commonly identified as a B2 carcinogen by the united states centers for disease control and the international cancer research institution, causing serious damage to the human kidney, bone marrow hematopoiesis, digestive system, nervous system, reproductive system, liver and brain. Therefore, the development of an efficient, green and sustainable repair strategy for treating the lead pollution site is urgently needed.
Traditional remediation strategies for heavy metal contaminated sites include physical, chemical and biological methods. The physical repair technology mainly removes pollutants from an environmental medium through a physical way, comprises a soil replacement method, thermal desorption, solidification and the like, and is suitable for large-area pollution treatment; the chemical remediation technology is mainly used for realizing the removal or stabilization treatment of heavy metals by adding chemical materials into a polluted medium, and comprises chemical leaching, oxidation reduction, electrochemical driving and the like; the bioremediation technology is mainly used for remedying the polluted environment through the metabolic activities of animals, plants or microorganisms, and has the advantages of environmental friendliness and low cost.
In recent years, novel environmental functional materials have come into existence, wherein nanometer zero-valent iron (nZVI) has been reported to have the potential of efficiently fixing heavy metals for the first time so as to be widely noticed by researchers due to the unique nanometer core-shell structure, high surface reactivity and good environmental compatibility. The surface of the nZVI has a large number of functional groups and active sites, and the iron core stores abundant electronegative ions and heavy goldHas excellent adsorption performance and reduction activity and has good application prospect in the field of environmental pollution. However, the nZVI particles are easy to agglomerate due to attractive force, so that the specific surface area and the reactivity are greatly reduced; during material synthesis, storage and transport, the surface of nZVI is usually coated with iron oxide (Fe) 2 O 3 、Fe 3 O 4 ) Or hydrophilic oxyhydroxide (FeOOH) to form a passivation film, which greatly reduces the adsorption and reduction efficiency, so that the method still has certain limitation in practical application.
Oxalate is an important low molecular weight organic acid in plant root secretion and consists of two carboxyl functional groups (-COOH). In many theoretical and experimental researches, successful modification of a nano zero-valent iron material by a carboxyl functional group is reported, and an oxygen atom and a carbon atom on the carboxyl can be connected with the nano zero-valent iron through substitution to increase a surface Fe-O-H active site and improve the structural stability of the modified nano material. The oxalate can participate in the complexation and precipitation reaction of lead ions, so that the possibility that the three processes of reduction, adsorption and coprecipitation of the oxalate modified nano zero-valent iron material in the treatment of the lead-containing polluted wastewater is high-efficiency and parallel is provided.
The invention discloses a dry-type synthesis method of a rice hull biochar loaded nano-iron material, which is a Chinese patent with an authorization publication number of CN 110833817A, wherein the material prepared by the method has a lasting and efficient repairing effect on hexavalent chromium contaminated soil, and the bioavailability of hexavalent chromium is remarkably reduced.
The invention discloses a rhamnolipid modified nano zero-valent iron and a preparation method and application thereof, and a material prepared by the method has high reactivity, stability, dispersibility and permeability and has no secondary pollution.
The invention discloses a preparation method of a microbial inoculum-CMC modified nano zero-valent iron, which is a Chinese patent with an authorization publication number of CN 111229153A, and the method remarkably reduces the dosage of the nano zero-valent iron and avoids the damage to a soil structure by screening strains with good synergistic performance with the CMC nano zero-valent iron.
The invention patent of China with the publication number of CN 111235059A discloses a modification synthesis process of microbial inoculum-SDS nanometer zero-valent iron, and the material prepared by the method can effectively inhibit particle agglomeration and avoid oxidation phenomenon generated by reaction with other media due to high active sites on the surface.
The invention discloses a Chinese patent with an authorization publication number of CN 105562708A, and discloses a nano zero-valent iron material for surface modification of p-hydroxyanisole (MEHQ) or polyelectrolyte Polyethyleneimine (PEI). The material has good dispersibility, stability and oxidation resistance, and reduces the agglomeration phenomenon of the nano zero-valent iron through steric hindrance and electrostatic steric hindrance.
Disclosure of Invention
In order to overcome the problems that the synthesized nano zero-valent iron in the prior art is easy to oxidize and agglomerate, the invention provides an oxalate modified nano zero-valent iron material and a preparation method thereof, wherein a proper molar ratio of Ox/Fe is controlled, the structural stability and the interface interaction of the nano zero-valent iron material are improved, and the oxalate modified nano zero-valent iron material is applied to the treatment of lead-containing wastewater, so that the removal effect of lead ions in water is improved.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
according to the first aspect of the invention, the oxalate modified nano zero-valent iron material is prepared from the following raw materials: ferric chloride hexahydrate, sodium borohydride and oxalate.
Further, the mass ratio of ferric chloride hexahydrate to oxalate is 5: 1-6: 1.
further, the average particle size of the oxalate modified nano zero-valent iron material is 100 nm.
According to a second aspect of the invention, a preparation method of the oxalate modified nano zero-valent iron material is provided, which comprises the following specific steps:
1) slowly injecting the sodium borohydride solution into a three-neck flask filled with ferric trichloride hexahydrate solution through an injector under the condition of introducing nitrogen gas protective atmosphere, adjusting the rotating speed of a magnetic stirrer to be 300r/min, and reacting for 30min at normal temperature to obtain a nano zero-valent iron suspension;
2) injecting oxalate solution into the suspension obtained in the step 1), and reacting for 30min at normal temperature to obtain oxalate modified nano zero-valent iron suspension;
3) and (3) carrying out vacuum filtration on the turbid liquid obtained in the step 2), repeatedly washing distilled water and absolute ethyl alcohol, drying in a vacuum drying oven at 80 ℃ for 12h, and grinding to obtain the oxalate modified nano zero-valent iron material.
Further, the concentration of the ferric trichloride hexahydrate solution in the step 1) is 0.1 mol/L.
Further, the concentration of the sodium borohydride solution in the step 1) is 0.3 mol/L.
Further, the oxalate solution in the step 2) is 0.1mol/L potassium oxalate or sodium oxalate solution, preferably 0.1mol/L potassium oxalate solution.
According to a third aspect of the invention, the oxalate modified nano zero-valent iron material is provided for application in treatment of lead-containing wastewater.
Furthermore, the oxalate modified nano zero-valent iron material has the effects of reduction, adsorption and coprecipitation on lead ions.
Compared with the prior art, the beneficial effects of the invention mainly include but are not limited to the following aspects:
(1) the preparation method adopts a one-step liquid phase reduction method, oxalate is selected as a modifier in the preparation process, the oxalate is blended in a mixed solution of ferric trichloride hexahydrate and sodium borohydride, the oxalate and iron ions are fully combined through magnetic stirring, and the mixture is dried in vacuum at the temperature of 80 ℃ to obtain the oxalate modified nano zero-valent iron material. Compared with the traditional liquid phase reduction method, the oxalate is easier to be substituted and connected with the surface active functional group of the nano zero-valent iron in the preparation process, so that the structural stability and the interface interaction of the oxalate modified nano zero-valent iron are enhanced.
(2) The oxalate modified nano zero-valent iron material prepared by the invention has rich reactive active sites and high-efficiency iron core electron transfer capability, overcomes the defects that nano zero-valent iron is easy to oxidize and agglomerate, exerts the advantage of oxalate for fixing heavy metal, can realize the aim of paralleling the three processes of reduction, adsorption and coprecipitation, and is an environmental function repairing material suitable for repairing water and soil pollution.
(3) The oxalate used in the invention is a plant root secretion which is widely existed in nature, the carboxyl functional group of the oxalate can be used as a medium for the interaction with the nano zero-valent iron material, and compared with most of chemical modification and doping methods, the oxalate modified nano zero-valent iron material prepared by the invention has the advantages of high stability, good biocompatibility, low price, easy obtaining, environmental friendliness and the like.
Drawings
In order to clearly understand the embodiments of the present invention or the technical solutions in the prior art, the following detailed descriptions will be provided with reference to the accompanying drawings which are used for describing the embodiments or the prior art. Several embodiments of the present disclosure are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:
FIG. 1 is a scanning electron microscope image of a nano zero-valent iron material before and after oxalate modification in example 2 of the present invention;
FIG. 2 is a Fourier infrared spectrum of the nano zero-valent iron material before and after oxalate modification in example 2 of the present invention;
FIG. 3 is an X-ray diffraction pattern of the nano zero-valent iron material before and after oxalate modification in example 2 of the present invention;
FIG. 4 shows the effect of oxalate modified nanoscale zero-valent iron on removing lead from a polluted water body at different reaction times in example 3 of the present invention;
FIG. 5 shows the effect of oxalate modified nanoscale zero-valent iron on removing lead from a polluted water body under different lead concentrations in example 4 of the present invention;
fig. 6 shows the removal effect of the oxalate modified nanoscale zero-valent iron material on lead in a polluted water body, which is prepared by the one-step method and the two-step method in example 5 of the present invention.
Detailed Description
The present invention is described in detail below by using specific embodiments, which are only used to explain the present invention, and those skilled in the art can refer to the embodiments and can modify the process parameters in different application scenarios. It is particularly emphasized that improvements in the parameters or process variations of the present invention are considered to be derivatives of the present invention without departing from the scope of the patent. The specific implementation case is as follows:
example 1
This example is the preparation of oxalate modified nanoscale zero-valent iron material.
25mL of 0.1M ferric chloride hexahydrate solution was placed in a 250mL three-necked flask with three openings connected to a magnetic stirrer, a nitrogen cylinder and a syringe, respectively. After a nitrogen bottle is opened and nitrogen is introduced for 5min, 30mL of 0.3M sodium borohydride solution is slowly injected into a three-neck flask through an injector, the rotating speed of a magnetic stirrer is adjusted to 300r/min, stirring is carried out for 30min at normal temperature, and the reaction formula is as follows:
under the condition of introducing a nitrogen protective atmosphere, slowly injecting 25ml of 0.1M sodium oxalate solution into a three-neck flask through a syringe, and continuously reacting at normal temperature for 30min to obtain a black mixture, wherein the reaction formula is as follows:
washing the black mixture by using a mixed solution of ethanol and deionized water (volume ratio is 1: 2), and carrying out vacuum drying at 80 ℃ for 12h to obtain a black solid product, namely the oxalate modified nano zero-valent iron.
Example 2
This example illustrates the chemical characterization of the product prepared in example 1 before and after reaction with lead.
A proper amount of the product is taken to be subjected to scanning electron microscope analysis on the appearance, and the obtained result is shown in figure 1. The nano zero-valent iron material is in a chain structure, the surface of the oxalate modified nano zero-valent iron material is covered by a film-shaped sheet, and the particle size of the material is below 100 nm.
Taking appropriate amount of product and performing Fourier transformThe functional groups were analyzed by external spectroscopy, and the results are shown in FIG. 2. The quantity and the types of functional groups on the surface of the oxalate modified nano zero-valent iron material are greatly increased, wherein 1608-1637cm -1 The peak indicates that the C ═ O group is increased, 460-581cm -1 The peak value indicates hematite (alpha-Fe) 2 O 3 ) To maghemite (Fe) 3 O 4 ) Transformation, 3500cm -1 The peak value shows that the carboxyl functional group of oxalate has substitution connection with the surface of the nano zero-valent iron.
The crystal structure was analyzed by X-ray diffraction of the appropriate amount of product, the results are shown in FIG. 3. The oxalate modified nano zero-valent iron material generates Fe 0 (2θ＝44.8°)、α-Fe 2 O 3 (2θ＝35.5°)、Fe 3 O 4 Characteristic diffraction peaks of (2 θ ═ 34.9 ° and 43.7 °). After reaction with lead, Fe 0 Reduced peak intensity, alpha-Fe 2 O 3 And Fe 3 O 4 The peak intensity increased and Pb appeared 0 Characteristic diffraction peaks (2 θ ═ 31.6 °, 36.4 °, 52.4, 62.2 °).
Example 3
The embodiment researches the removal effect of oxalate modified nano zero-valent iron on lead in the polluted water body under different reaction times.
The lead-containing wastewater used in this example was prepared from lead nitrate. Preparing a lead nitrate solution with the concentration of 400mg/L, and adjusting the pH value of the solution to 7.0. Adding oxalate modified nano zero-valent iron in an adding amount of 1.44g/L, and placing the mixture in a constant temperature oscillation box to oscillate for 48 hours at 25 ℃ and the rotating speed of 200 rpm. And (3) starting timing by self-adding oxalate modified nano zero-valent iron, collecting supernatant at 5, 10, 15, 30, 60, 120, 240, 480, 720 and 1440min, and measuring the lead content in the solution after reaction by adopting a flame atomic absorption spectrophotometer.
And (4) analyzing results:
FIG. 4 is a diagram showing the effect of oxalate modified nano zero-valent iron on the removal of lead from a solution. From fig. 4, the removal efficiency of oxalate modified nano zero-valent iron on lead in the solution is close to 100%, and the lead removal efficiency is substantially balanced in 400min, while the removal efficiency of unmodified nano zero-valent iron is only 63.6%.
Example 4
The embodiment researches the removal effect of oxalate modified nano zero-valent iron on lead in the polluted water body under different lead concentration conditions.
The lead-containing wastewater used in this example was prepared from lead nitrate. Lead nitrate solutions with the concentrations of 200, 300, 400 and 500mg/L are prepared, and the pH value of the solution is adjusted to 7.0. Adding 0.56g/L of oxalate modified nano zero-valent iron, and placing the nano zero-valent iron in a constant temperature oscillation box to oscillate for 48 hours at 25 ℃ and the rotating speed of 200 rpm. And (3) measuring the content of lead in the solution after reacting for 24 hours by using a flame atomic absorption spectrophotometer.
And (4) analyzing results:
FIG. 5 is a diagram showing the effect of oxalate modified nanoscale zero-valent iron on removal of lead in solution at different concentrations. As can be seen from FIG. 5, the saturated adsorption amount of oxalate modified nano zero-valent iron material to lead in the solution is up to 429mg/g, while the saturated adsorption amount of unmodified nano zero-valent iron to lead in the solution is only 153 mg/g.
Example 5
This example explores the removal effect of oxalate modified nanoscale zero-valent iron prepared by one-step and two-step methods on lead in polluted water.
The difference from example 1 is that under the protection of nitrogen, 50mL of 0.1M ferric trichloride hexahydrate solution and 50mL of 0.6M potassium borohydride solution are mixed and stirred for 30min, a black mixture is washed by a mixed solution of ethanol and deionized water (volume ratio is 1: 2), a black solid product is obtained after vacuum drying for 12h at 80 ℃, 100mL of 0.1M sodium oxalate solution is injected for continuous reaction for 1h, and oxalate modified nano zero-valent iron synthesized by a two-step method is obtained. The other steps remain unchanged.
In the same way as example 3, the removal effect of the oxalate modified nano zero-valent iron synthesized by the one-step method and the two-step method under different reaction times on lead in the polluted water body is explored.
And (4) analyzing results:
FIG. 6 is a diagram showing the effect of oxalate modified nanoscale zero-valent iron prepared by a one-step method and a two-step method on removal of lead in a solution. As can be seen from FIG. 6, the one-step oxalate modified nanoscale zero-valent iron exhibits a faster reaction rate, and reaches equilibrium substantially within 400min, while the two-step oxalate modified nanoscale zero-valent iron reaches equilibrium within 700 min.
The above embodiments are not intended to limit the present invention, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and fall within the scope of the present invention.
Claims (10)
1. The preparation method of the oxalate modified nano zero-valent iron material is characterized by comprising the following preparation raw materials: ferric chloride hexahydrate, sodium borohydride and oxalate.
2. The preparation method according to claim 1, comprising the following specific steps:
1) slowly injecting the sodium borohydride solution into a three-neck flask filled with ferric trichloride hexahydrate solution through an injector under the condition of introducing nitrogen gas protective atmosphere, adjusting the rotating speed of a magnetic stirrer to be 300r/min, and reacting for 30min at normal temperature to obtain a nano zero-valent iron suspension;
2) injecting oxalate solution into the suspension obtained in the step 1), and reacting for 30min at normal temperature to obtain oxalate modified nano zero-valent iron suspension;
3) and (3) carrying out vacuum filtration on the turbid liquid obtained in the step 2), repeatedly washing distilled water and absolute ethyl alcohol, drying in a vacuum drying oven at 80 ℃ for 12h, and grinding to obtain the oxalate modified nano zero-valent iron material.
3. The method for preparing the oxalate modified nano zero-valent iron material according to claim 2, wherein the concentration of the ferric trichloride hexahydrate solution in the step 1) is 0.1 mol/L; the concentration of the sodium borohydride solution is 0.3 mol/L.
4. The method for preparing the oxalate modified nano zero-valent iron material according to claim 2, wherein the oxalate solution in the step 2) is 0.1mol/L potassium oxalate or sodium oxalate solution, preferably 0.1mol/L potassium oxalate solution.
5. The method for preparing the oxalate modified nano zero-valent iron material according to claim 2, wherein the mass ratio of ferric trichloride hexahydrate to oxalate is 5: 1-6: 1.
6. an oxalate modified nano zero-valent iron material which is obtained by the preparation method of any one of claims 1 to 5.
7. The oxalate modified nanoscale zero-valent iron material of claim 6, wherein the carboxyl functional group of oxalate increases electronegative ions and active sites on the surface of nanoscale zero-valent iron, thereby enhancing the structural stability and interfacial interaction of oxalate modified nanoscale zero-valent iron material.
8. The oxalate modified nanoscale zero-valent iron material of claim 6, wherein the oxalate modified nanoscale zero-valent iron material has an average particle size of 300 nm.
9. The use of the oxalate modified nanoscale zero-valent iron material of claim 6 in the treatment of lead-containing wastewater.
10. The use of the oxalate modified nanoscale zero-valent iron material of claim 9, wherein the oxalate modified nanoscale zero-valent iron material has the effects of reducing, adsorbing and coprecipitating lead ions.
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