CN109174196B - Preparation method of chelate resin loaded copper-iron bimetallic nano-material - Google Patents
Preparation method of chelate resin loaded copper-iron bimetallic nano-material Download PDFInfo
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- CN109174196B CN109174196B CN201810914083.3A CN201810914083A CN109174196B CN 109174196 B CN109174196 B CN 109174196B CN 201810914083 A CN201810914083 A CN 201810914083A CN 109174196 B CN109174196 B CN 109174196B
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 62
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013522 chelant Substances 0.000 title claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920001429 chelating resin Polymers 0.000 claims abstract description 42
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 15
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims 1
- 229910002549 Fe–Cu Inorganic materials 0.000 abstract description 41
- 239000003054 catalyst Substances 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000002114 nanocomposite Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910017827 Cu—Fe Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000040710 Chela Species 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- -1 nZVI Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical class ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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Images
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/23—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/02—Preparation of nitrogen
Abstract
The invention discloses a preparation method of a chelate resin loaded copper-iron bimetallic nano material, relates to the field of preparation of reduced nitrate nano composite materials, and comprises the step 1 of preparing adsorbed Cu2+The chelating resin of (a); step 2, preparing a Fe-Cu/D407 bimetal nano material; and 3, washing and drying the final product obtained in the step 2. The invention has the advantages that: (1) the nano material prepared by the method of the invention firstly puts Cu into2+The double metal catalyst is fixedly adsorbed on chelate resin and then prepared by a one-step liquid phase reduction method; (2) the Fe-Cu/D407 bimetallic nano material prepared by the method can react with NO when the ratio of Cu to Fe is 1:23 ‑The removal rate of the catalyst is up to more than 99 percent, and the catalyst is used for N2The selectivity of the nitrate is as high as 89.7 percent, and the nitrate has extremely high-efficiency performance of reducing nitrate and high-selectivity performance of reducing nitrate into nitrogen.
Description
Technical Field
The invention relates to the field of preparation of reduced nitrate nano composite materials, in particular to a preparation method of a chelate resin loaded copper-iron bimetallic nano material.
Background
In recent years, with the development of agriculture and industry, the nitrate content in water is increasing and the nitrate content tends to deteriorate. Excess NO in drinking water3 -Is a potentially harmful substance because it may have an adverse effect on human health. Nitrate is easy to react with hemoglobin to form methemoglobin after entering a human body, and the transmission capability of blood to oxygen is influenced. In addition, nitrite can form highly carcinogenic nitrosamines and nitrosamides in the stomach and trigger mutagenesis. With the increasing shortage of water resources and the serious pollution problem of nitrate in many areas of China, the pollution of nitrate in water is eliminated. Thus, the world health organization (WH0) has been converting NO in drinking water3 --N、NO2 --N and NH4 +-N are each defined as 10mgL-1、0.03mgL-1And 0.4mgL-1. Various techniques have been developed to treat contaminated NO3 -The water of (2). Ideally NO3 -Should be selectively reduced to N2Rather than further reduction to NH4 +. Biological denitrification, catalytic hydrogenation and photocatalytic reduction are used for selectively reducing nitrate into nontoxic N2An effective technique of (1). Biological denitrification, i.e. biological denitrification, is carried out by stepwise formation of N2The effective method for removing the nitrate is sensitive to the change of treatment conditions such as dissolved oxygen, temperature and dissolved organic matters, the process for removing the nitrate by the biological method is slow, and NO can be released when the treatment is incomplete2 -、NOXAnd N2O, and simultaneously generates a large amount of biological sludge to be subsequently treated. Catalytic hydrogenation reduction, i.e., catalytic reduction of nitrates with a noble metal catalyst. At present, the method mostly adopts hydrogen as a reducing agent, and loads a metal catalyst on a certain carrier, so that the generation of harmful reduction products of ammonia nitrogen and nitrite nitrogen can be reduced, nitrate is reduced into harmless nitrogen, and the nitrogen has high N2Selectivity, but this technique requires hydrogen as a reducing agent or electron donor, with potential safety issues arising during the transport and use of pressurized hydrogen, while the use of noble metals as catalysts limits its use to a wide range of applications. The photocatalytic reduction process can utilize solar energy to remove nitrates, but ammonia formation is an undesirable end product.
In recent years, chemical reduction has been considered as a very effective method for degrading nitrate, in which nitrate can be converted into nitrite, ammonia nitrogen and nitrogen, and particularly, a chemical method based on nano zero-valent iron (nZVI), which is widely used to effectively convert various pollutants in water, including various reductions on nitrate, due to its excellent electron donating ability, wide iron sources, low price and friendly environment. Many studies have shown that nZVI can be considered a non-noble metal catalyst for the chemical reduction of nitrates. However, nZVI also shows the obvious disadvantage of poor dispersion, easy deactivation under operating conditions, leading to rapid loss of reactivityLow stability and high processing cost. Thus, several strategies to enhance the reduction of nitric acid to N have been reported in current research2The efficiency of (c). For example, Fe, Pd and Cu form Fe0/(Fe/Cu)、 Cu-nFe0Clinoptilolite and (Pd-Cu) -nFe0Iso-bimetallic or tri-metallic catalytic materials for selective catalytic hydrogenation of nitrates to produce N2The method has good effect. However, they have disadvantages in that hydrogen is used and the reaction speed is extremely slow.
Therefore, to increase N2The present invention has been made in an effort to develop a method for preparing a chelate resin-supported copper-iron bimetallic nanomaterial, which has high efficiency of removing nitrate and high selectivity of producing N2In addition, the removal rate of nitrate and the selectivity of reducing the nitrate into N2 can be improved only by properly controlling the pH value and the reaction temperature of the reaction solution, so that the method has great market value and application potential.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a method for preparing a chelating resin supported copper-iron bimetallic nanomaterial, which can improve the selectivity of N2 and avoid the use of hydrogen, the method for preparing the chelating resin supported copper-iron bimetallic nanomaterial for the first time, the material has the functions of efficiently removing nitrate and generating N2 with high selectivity, and in addition, the removal rate of nitrate and the selectivity of reducing the nitrate into N2 can be improved only by properly controlling the pH value and the reaction temperature of the solution, so the method has great market value and application potential.
In order to achieve the above object, the present invention provides a method for preparing a chelating resin loaded copper-iron bimetallic nanomaterial, comprising the steps of:
step 4, transferring the reaction solution in the second container to a third container, introducing N2 into the third container to remove dissolved oxygen in the solution while adding potassium borohydride under mechanical stirring, and obtaining a black precipitate after the reaction is finished;
and 5, respectively washing the black precipitate obtained in the step 4 in oxygen-free water and absolute ethyl alcohol for multiple times, carrying out suction filtration, and then transferring the black precipitate to a vacuum drying oven for drying to obtain the final product, namely the chelating resin loaded copper-iron bimetallic nano material.
Further, the mass of the copper sulfate pentahydrate added in the step 1 is 0.2-0.6 g.
Further, the mass of the chelating resin added in the step 2 is 1-2 g.
Further, the temperature of constant temperature oscillation in the step 2 is 30-40 ℃, and the oscillation time is 10-12 h.
Further, the weight of the ferrous sulfate heptahydrate added in the step 3 is 0.6-1.0 g.
Further, the temperature of constant temperature oscillation in the step 3 is 30-40 ℃, and the oscillation time is 10-12 h.
Further, the volume of the potassium borohydride in the step 4 is 10-20mL, and the concentration is 30-50 g/L.
Further, in the step 5, the drying temperature is set to be 70-80 ℃ in a vacuum drying oven, and the drying time is 24-26 h.
Further, the application of the chelate resin loaded copper-iron bimetallic nano material prepared by the preparation method of the chelate resin loaded copper-iron bimetallic nano material in removing nitrate and reducing the nitrate into N2 with high selectivity is provided.
Compared with the prior art, the method of the invention has the advantages that:
(1) the nano material prepared by the method of the invention firstly puts Cu into2+Is immobilized and adsorbed on chelating resin (D407), and is the first time that the resin porous material is used for removing NO3In the material, the bimetallic catalyst is prepared by a one-step liquid phase reduction method, and the synergistic action mechanism of Cu and Fe is clarified for the first time;
(2) the Fe-Cu/D407 bimetallic nano material prepared by the method can react with NO when the ratio of Cu to Fe is 1:23The removal rate of the nitrate is up to more than 99 percent, the selectivity of the nitrate to N2 is up to 89.7 percent, and the nitrate has extremely high-efficiency performance of reducing nitrate and high-selectivity performance of reducing the nitrate into nitrogen;
(3) the preparation method provided by the invention is simple and feasible, the production cost is low, and the prepared nano material has high purity.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a flow chart of the preparation of a preferred embodiment of the present invention;
FIGS. 2(a) to 2(b) are XRD contrast diagrams before and after reflection of a chelating resin loaded copper-iron bimetallic nanomaterial, Fe-Cu nanomaterial, nZVI nanomaterial and nitrate prepared by a preferred embodiment of the present invention;
FIGS. 3(a) to 3(d) show the preparation of chelating resin loaded Cu-Fe bimetallic nanomaterial and Fe-Cu, nZVI nanomaterial pair NO prepared according to a preferred embodiment of the present invention3The removal efficiency and the selectivity of the product are compared and the chelating resin loaded copper-iron bimetallic nano material with different Cu/Fe ratios is used for NO3A graph comparing the removal efficiency with the selectivity of the product of (1);
FIGS. 4(a) to 4(d) are SEM images of Cu-Fe bimetallic nanomaterials loaded with chelating resins of different Cu/Fe ratios prepared according to a preferred embodiment of the present invention;
FIG. 5 is a diagram illustrating the mechanism of reduction of nitrate by the copper-iron bimetallic nanomaterial loaded on the chelating resin prepared by the preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
As shown in fig. 1, a flow chart of a preferred embodiment of the present invention, a method for preparing a chelating resin loaded copper-iron bimetallic nanomaterial comprises the following steps:
step 1: weighing 0.2-0.6g of blue vitriol, adding into a first container, adding a proper amount of deionized water to completely dissolve blue vitriol, weighing 1.0-2.0g of chelating resin (D407), adding into the first container, placing the first container in a constant temperature oscillator, setting the temperature at 30-40 ℃, oscillating for 10-12h to obtain the adsorbed Cu2+Then washing the chelate resin with deionized water for a plurality of times;
step 2: weighing 0.6-1.0g of ferrous sulfate heptahydrate, adding into a second container, adding a proper amount of deionized water to completely dissolve the ferrous sulfate heptahydrate, and adsorbing Cu obtained in the step 12+Adding the chelate resin particles into a second container, placing the second container into a constant-temperature oscillator, setting the temperature to be 30-40 ℃, and oscillating for 10-12h to obtain a mixed solution;
and step 3: and transferring the solution in the second container to a third container, introducing N2 into the third container to remove dissolved oxygen in the solution under the action of mechanical stirring, dropwise adding 10-20mL of 30-50g/L potassium borohydride into the third container while reacting to obtain a black precipitate, washing the black precipitate for multiple times respectively with oxygen-free water and absolute ethyl alcohol, carrying out suction filtration, and transferring the black precipitate to a vacuum drying oven for drying to obtain the final product, namely the chelating resin loaded copper-iron bimetallic nano material.
Example 1 preparation of chelate resin-loaded copper-iron bimetallic nanomaterial
Step 1: 0.3901g of copper sulfate pentahydrate are weighed into a 50mL conical flask, 25mL of deionized water is added into the conical flask to completely dissolve the copper sulfate pentahydrate, and 1g of chela is weighedMixing resin (D407) in the conical flask, placing the conical flask in a constant temperature oscillator, setting the temperature at 30 ℃, and oscillating for 12h to obtain adsorbed Cu2+Then washing the chelating resin adsorbing Cu2+ with deionized water for 3 times;
step 2: 0.8688g of ferrous sulfate heptahydrate were weighed into a 50mL Erlenmeyer flask, 25mL of deionized water was added to the Erlenmeyer flask to completely dissolve the ferrous sulfate heptahydrate, and the adsorbed Cu obtained in step 1 was added2+Adding the chelate resin particles into a conical flask, placing the conical flask in a constant temperature oscillator, setting the temperature at 30 ℃, and oscillating for 12 hours at the rotating speed of 200 r/min.
And step 3: and (3) transferring the solution obtained in the step (2) into a 250mL four-neck flask, introducing N2 to remove dissolved oxygen in the solution under the mechanical stirring action of 400rpm, dropwise adding 15mL 50g/L potassium borohydride solution into the four-neck flask while reacting, respectively washing the obtained black precipitate for 3 times by using oxygen-free water and absolute ethyl alcohol respectively after the reaction is finished, carrying out suction filtration, transferring the black precipitate into a vacuum drying oven, setting the temperature at 80 ℃ and drying for 24 hours to obtain the final product, namely the chelating resin loaded copper-iron bimetallic nano material. Under other conditions, the chelating resin loaded copper-iron bimetallic nano-material with different Cu/Fe ratios can be prepared by changing the amount of the blue vitriol.
For comparison experiments, the inventor also implements the following 2 examples to prepare the Fe-Cu bimetal nano material and the nano zero-valent iron, and the specific preparation process is as follows:
example 2
Preparation of Fe-Cu bimetal nano material
In the embodiment, a liquid phase reduction method is adopted to prepare the Fe-Cu bimetal nano material, and the steps are as follows: 5.6g of ferrous sulfate heptahydrate and 2.5g of copper sulfate pentahydrate were weighed out and completely dissolved in 100mL of deionized water, and transferred to a 250mL four-necked flask, and N2 was continuously introduced to remove dissolved oxygen from the solution under mechanical stirring at 400 rpm. Then 3.5g of potassium borohydride is weighed and dissolved in 50mL of deionized water to prepare a potassium borohydride solution, and then the potassium borohydride solution is dripped into the four-neck flask. After the reaction is finished, washing the obtained black precipitate respectively with oxygen-free water and absolute ethyl alcohol for 3 times, carrying out suction filtration, and drying the black precipitate in a vacuum drying oven at the set temperature of 70 ℃ for 26 hours to obtain the product Fe-Cu bimetallic nano material. Under the condition that other conditions are not changed, Fe-Cu bimetallic nano-materials with different Cu/Fe ratios can be prepared by changing the amount of the blue vitriol.
Example 3
Preparation of nano zero-valent iron (nZVI)
Weighing 5.6g of ferrous sulfate heptahydrate to be dissolved in 100mL of deionized water, transferring the ferrous sulfate heptahydrate solution to a 250mL four-neck flask, introducing N2 all the time to remove dissolved oxygen in the solution under the action of mechanical stirring at 400rpm, weighing 3g of potassium borohydride to be dissolved in 50mL of deionized water to prepare a potassium borohydride solution, and then dropping the potassium borohydride solution into the four-neck flask. After the reaction is finished, washing the obtained black precipitate respectively with anaerobic water and absolute ethyl alcohol for 3 times, carrying out suction filtration, and finally drying the black precipitate in a vacuum drying oven at the set temperature of 70 ℃ for 24 hours to obtain the product nano zero-valent iron nZVI.
The following are characterization and experimental comparisons of materials prepared by the methods of the examples of the invention.
As shown in fig. 2(a) to 2(b) XRD comparison graphs before and after reaction of the chelating resin loaded copper-iron bimetal nanomaterial prepared according to a preferred embodiment of the present invention, Fe-Cu, nZVI nanomaterial, and nitrate, in fig. 2(a), a diffraction peak of Cu appears near 43.3 ° in Fe-Cu/D407 and a diffraction peak of Fe appears near 45 ° before the reaction; the Fe-Cu bimetal nano composite material has Cu diffraction peaks at the attachments of 43.3 degrees and 50.4 degrees, and has Fe diffraction peaks near 45 degrees; the nZVI nano material shows a diffraction peak of Fe near 45 degrees. In FIG. 2(b), it can be seen that Fe-Cu/D407 appeared near 35.5 °, 57 ° and 62.5 ° after the reaction2O3The diffraction peak of (2) shows a diffraction peak of Cu near 43.3 DEG, and the diffraction peak of Fe disappears; Fe-Cu bimetal nano composite material also has Fe in the vicinity of 35.5 degrees, 57 degrees and 62.5 degrees2O3The diffraction peak of (2) shows a diffraction peak of Cu near 43.3 DEG, and the diffraction peak of Fe disappears; the nZVI nano material has a diffraction peak of Fe near 45 degrees, butThe intensity of the diffraction peak is reduced greatly compared with that before the reaction. From this it can be concluded that: the prepared Fe-Cu/D407 and Fe-Cu bimetallic nano-materials have good crystallinity, the crystallization performance of nZVI is poor, Fe (0) and Cu (0) peaks can be observed in XRD patterns of Fe-Cu/D407 and Fe-Cu, and the Fe-Cu bimetallic nano-materials meet the standard cards of Fe (JCPDS #03-1050) and Cu (JCPDS # 85-1326). Elemental analysis showed that only Fe, Cu and D407 were indeed present in the Fe-Cu/D407 composite. In addition, with NO3After 120mins of reaction, XRD of the Fe-Cu/D407 composite material and the Fe-Cu bimetal nano composite material has obvious change, and Fe (0) is almost not generated after the reaction, which shows that Fe (0) participates in the reaction and is greatly consumed to generate Fe2O3(JCPDS302-1047), which indicates that the addition of Cu changes the reduction of NO by nZVI3The path of (2).
The Fe-Cu/D407 and Fe-Cu, nZVI nano-materials prepared according to a preferred embodiment of the present invention as shown in FIGS. 3(a) to (D) are NO3The removal efficiency and the selectivity of the product are compared and the chelating resin prepared by different Cu/Fe ratios carries the copper-iron bimetallic nano material to NO3The removal efficiency and the selectivity of the product are shown in the graph, wherein, in the graph of fig. 3(a) and fig. 3(b), chelating resin loaded copper-iron bimetallic nano-material with different Cu/Fe ratios is used for NO3FIG. 3(c) and FIG. 3(D) are graphs of the removal efficiency of (1) and the selectivity of various products for NO versus Fe-Cu/D407, Fe-Cu, nZVI, Cu/D407 and D407 nanomaterials3FIG. 3(a) and FIG. 3(b) show the removal efficiency pattern and selectivity pattern of various products, where Cu: Fe is 2: 1, Fe-Cu/D407 vs. NO3The removal rate of the catalyst reaches about 58 percent, and the selectivity of the catalyst to N2 reaches about 34 percent; Fe-Cu/D407 to NO when Cu: Fe is 1: 13The removal rate of the catalyst reaches about 48 percent, and the selectivity of the catalyst to N2 reaches about 40 percent; Fe-Cu/D407 to NO when Cu: Fe is 1: 33The removal rate of the catalyst reaches about 97 percent, and the selectivity of the catalyst to N2 reaches about 48 percent; Fe-Cu/D407 to NO when Cu: Fe is 1:23The removal rate of the catalyst is up to more than 99 percent, and the selectivity of the catalyst to N2 is up to 89.7 percent. FIG. 3(c) shows that Fe-Cu/D407 vs NO in 5 kinds of materials, Fe-Cu/D407 composite material, Fe-Cu bimetal nanomaterial, nZVI, Cu/D407, and D4073The removal rate is highest and can reachMore than 99 percent, and the highest selectivity of the Fe-Cu/D407 composite material to N2 in the three materials of the Fe-Cu/D407 composite material, the Fe-Cu bimetallic nano material and the nZVI material can be seen from the graph in FIG. 3(D), and can reach 89.7 percent. The method is mainly characterized in that the chelating resin (D407) provides a good carrier for the Fe-Cu bimetallic nano material, and meanwhile, due to the potential difference between Fe and Cu, a plurality of miniature primary batteries are formed between Fe and Cu to accelerate the corrosion of nZVI and improve the reduction efficiency of nitrate, and NO2 is easier to adsorb on the surface of Cu, so that the generation rate of N2 is improved. Therefore, in summary, when Cu and Fe are 1 to 2, Fe-Cu/D407 nano material NO3The selective reduction to N2 was most effective.
As shown in fig. 4(a) to 4(d), SEM images of copper-iron bimetallic nanomaterial loaded on chelating resin with different Cu/Fe ratios prepared according to a preferred embodiment of the present invention are shown, wherein, in fig. 4 (a): Cu/Fe is 2: 1; fig. 4 (b): Cu/Fe is 1: 1; fig. 4 (c): Cu/Fe is 1: 2; fig. 4 (d): as can be seen from fig. 4(a) to 4(D), as the mass fraction of copper decreases, the surface of the spherical nano zero-valent iron particles becomes irregular and even the morphology collapses, resulting in a decrease in the reactivity of the Fe-Cu/D407 catalyst. The result shows that the addition of copper has important influence on the shape and the reactivity of the Fe-Cu/D407.
As shown in FIG. 5, which is a mechanism diagram of the chelate resin supported copper-iron bimetallic nanomaterial of the present invention for reducing nitrate, nZVI acts as an electron donor of the second metal Cu, NO, due to the relative redox potential difference between Fe and Cu3Firstly, the Fe surface is reduced into N2 and NH4 +And NO2, Fe itself being oxidized to Fe2+ or Fe2O3. And the copper surface has high affinity to nitrite, so that an adsorbed species [ Cu-NO ] can be formed2ads]Further with [ Cu-H ]ads]A reaction takes place, after which nitrite is further reduced to ammonia, nitrogen and nitrogen. The chemical reaction equation involved is as follows:
Fe0+2H+→Fe2++H2under acid condition(1)
Fe0+2H2O→Fe2++2OH+2H2under neutral or alkaline condition(2)
2Cu+H2→2Cu-Hads(8)
the foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. A preparation method of a chelating resin loaded copper-iron bimetallic nano-material comprises the following steps:
step 1, weighing copper sulfate pentahydrate, adding the copper sulfate pentahydrate into a first container, and adding proper deionized water until the copper sulfate pentahydrate is completely dissolved;
step 2, weighing the chelating resin, adding the chelating resin into a first container, placing the first container in a constant temperature oscillator for oscillation, and obtaining the adsorbed Cu2+The chelate resin is then washed with deionized water for a plurality of times;
step 3, weighing ferrous sulfate heptahydrate, adding the ferrous sulfate heptahydrate into a second container, adding proper deionized water until the ferrous sulfate heptahydrate is completely dissolved, and adding the adsorbed Cu obtained in the step 2 into the second container2+And placing the second container in a constant temperature oscillator for oscillation;
step 4, transferring the reaction solution in the second container to a third container, and introducing N into the third container while mechanically stirring2Removing dissolved oxygen in the solution, adding potassium borohydride while reacting to obtain a black precipitate;
and 5, respectively washing the black precipitate obtained in the step 4 in oxygen-free water and absolute ethyl alcohol for multiple times, performing suction filtration, and then transferring the black precipitate to a vacuum drying oven for drying to obtain a final product, namely the chelating resin loaded copper-iron bimetal nano material, wherein the chelating resin is D407 type resin, and the mass ratio of copper to iron is 1: 2.
2. The method for preparing the chelating resin supported copper-iron bimetallic nanomaterial as claimed in claim 1, wherein the mass of the copper sulfate pentahydrate added in the step 1 is 0.2-0.6 g.
3. The method for preparing the chelating resin supported copper-iron bimetallic nanomaterial according to claim 1, wherein the mass of the chelating resin added in the step 2 is 1-2 g.
4. The method for preparing the chelating resin loaded copper-iron bimetallic nanomaterial according to claim 1, wherein the constant-temperature oscillation in the step 2 is performed at 30-40 ℃ for 10-12 h.
5. The method for preparing the chelating resin supported copper-iron bimetallic nanomaterial according to claim 1, wherein the weight of the ferrous sulfate heptahydrate added in the step 3 is 0.6-1.0 g.
6. The method for preparing the chelating resin loaded copper-iron bimetallic nanomaterial according to claim 1, wherein the constant-temperature oscillation in the step 3 is performed at 30-40 ℃ for 10-12 h.
7. The method for preparing the chelating resin loaded copper-iron bimetallic nanomaterial according to claim 1, wherein the volume of the potassium borohydride in the step 4 is 10-20mL, and the concentration is 30-50 g/L.
8. The method for preparing the chelating resin supported copper-iron bimetallic nanomaterial according to claim 1, wherein in the step 5, the drying temperature is set to 70-80 ℃ and the drying time is 24-26h in a vacuum drying oven.
9. The chelating resin loaded copper-iron bimetal nano material prepared by the preparation method of the chelating resin loaded copper-iron bimetal nano material as claimed in any one of claims 1 to 8, which is used for removing nitrate and reducing the nitrate into N with high selectivity2The use of (1).
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| CN103755004A (en) * | 2014-01-28 | 2014-04-30 | 哈尔滨工业大学 | Strong acid resin composite material of load zero-valence composite metal, preparation method and application thereof |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
| CN104226333A (en) * | 2014-09-26 | 2014-12-24 | 南京大学 | Preparation method for loaded nano iron-palladium bimetallic composite material and application method of material in selectively reducing nitrate |
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| CN102335628A (en) * | 2011-07-21 | 2012-02-01 | 南京大学 | Load-type nanometer duplex metal composite catalyst and preparation method thereof |
| CN103755004A (en) * | 2014-01-28 | 2014-04-30 | 哈尔滨工业大学 | Strong acid resin composite material of load zero-valence composite metal, preparation method and application thereof |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
| CN104226333A (en) * | 2014-09-26 | 2014-12-24 | 南京大学 | Preparation method for loaded nano iron-palladium bimetallic composite material and application method of material in selectively reducing nitrate |
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