CN113582284A - Preparation method of porous carbon loaded zero-valent iron composite material - Google Patents
Preparation method of porous carbon loaded zero-valent iron composite material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 29
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- 238000001354 calcination Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
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- 239000000843 powder Substances 0.000 claims description 5
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 description 7
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- 239000011148 porous material Substances 0.000 description 6
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
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- 239000003638 chemical reducing agent Substances 0.000 description 3
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- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 230000002588 toxic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 235000013980 iron oxide Nutrition 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 206010028813 Nausea Diseases 0.000 description 1
- YFMDUDVWFBWDGV-UHFFFAOYSA-N [B].[Fe].[Rb].[Fe] Chemical compound [B].[Fe].[Rb].[Fe] YFMDUDVWFBWDGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 229910052785 arsenic Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Images
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps: (1) mixing neodymium iron boron tailings and a carbon material, sequentially adding a pore-forming agent and alcohol, and stirring to obtain a mixed primary material; (2) and (2) sequentially carrying out ultrasonic treatment, drying and roasting on the mixed primary material obtained in the step (1) to obtain the porous carbon loaded zero-valent iron composite material. According to the preparation method of the zero-valent iron composite material, the high-performance lead adsorption composite material is prepared by adopting the specific raw materials and utilizing the rare earth elements in the raw materials. The prepared composite material has the characteristics of good dispersibility, uniform load, large specific surface area, good stability and the like.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a preparation method of a porous carbon loaded zero-valent iron composite material.
Background
With the rapid development of the industry in China, a large amount of toxic and harmful substances are discharged into water, and the pollution problem of heavy metals is more and more serious. Heavy metal ions such as lead, cadmium, mercury, chromium, metalloid arsenic and the like in the water body have obvious lasting toxic action on human, animals, plants and microorganisms. These heavy metals are not only not degraded by microorganisms but also enriched in organisms, especially in the human body, to produce more serious toxic effects. When the composition is accumulated to a certain content, a series of symptoms such as dizziness, nausea, arthralgia, amnesia and the like can appear on a human body, and the composition has great harm to the human body. Common techniques for removing heavy metals from water bodies include adsorption, membrane separation, electrochemical methods, chemical precipitation, and the like.
In recent years, nano zero-valent iron (nZVI) has been widely used in research on removal of heavy metals due to its advantages such as high specific surface area, excellent adsorption and reactivity. Research shows that the electrode potential of the zero-valent iron is-0.44V, and the reduction capability is strong; the heavy metal with metal activity ranked behind zero-valent iron can be directly replaced and attached to the surface of the zero-valent iron. Therefore, the nZVI can realize effective removal of heavy metals in the water body through two ways and mechanisms of adsorption and reduction.
For example, CN103253757A discloses a method for deeply treating complex industrial wastewater by using nano zero-valent iron. Aiming at the problems of complex composition, high concentration of pollutants, unstable water quality and the like of the existing industrial wastewater, the invention adopts a multistage series-connected nano zero-valent iron reaction device to carry out advanced treatment on the complex industrial wastewater, wherein the nano zero-valent iron is recycled in the device and reversely flows back step by step between the devices. Which is provided with a two to five-level nanometer zero-valent iron reaction device according to the number and concentration of pollutants contained in the actual wastewater. In the treatment process, the pH of each stage is controlled by adding acid/alkali and is gradually increased, the oxidation-reduction potential (ORP) of each stage is controlled by adding/refluxing nano zero-valent iron and is gradually decreased, and the wastewater is effectively treated after multi-stage reaction/separation. Can remove various pollutants in the wastewater step by step, has controllable reaction conditions at all stages, can stably reach the standard of the effluent quality, simultaneously improves the utilization rate of the nano zero-valent iron, and is suitable for advanced treatment of various complex industrial wastewater.
For example, CN104609531A discloses a preparation method of citrate nano zero-valent iron and a method for treating organic wastewater by activating persulfate. The method for treating organic wastewater comprises the following steps: adding peroxydisulfate and citrate stabilized nano zero-valent iron to wastewater containing organic pollutants; uniformly mixing the citrate-stabilized nanoscale zero-valent iron and the peroxydisulfate, wherein the citrate-stabilized nanoscale zero-valent iron releases ferrous ions and the zero-valent iron reacts with the peroxydisulfate to generate oxidizing free radicals which degrade organic pollutants in the wastewater, and the problem that the activation conditions of the peroxydisulfate activated by heating and light radiation in the prior art are complicated is solved through the method; when the ferrous ions are adopted to activate the peroxydisulfate, the ferrous ions react with active free radicals, so that the utilization rate of peroxysulfate radicals is reduced, and a large amount of iron mud is generated; at least partially overcomes the technical problem that the nano zero-valent iron is not easy to recover when the nano zero-valent iron activates the peroxydisulfate.
Currently, the process for preparing nZVI involves: liquid phase reduction method, carbothermic method, electrochemical deposition method, carbonyl iron pyrolysis method and green synthesis method. Among them, the liquid phase reduction method and the carbothermic reduction method are more commonly used, and the green synthesis method is a hot spot of recent research. The liquid phase reduction method is to utilize sodium borohydride/potassium borohydride and other strong reducing agents to reduce Fe in the state of solution2+Or Fe3+Reduction to Fe0. The liquid phase reduction method has simple and rapid preparation process and mild reaction conditions, and the prepared nZVI has high reaction activity and is the most widely applied preparation process. However, the liquid-phase reduction method requires the use of strong reducing agents such as sodium borohydride/potassium borohydride and the like and generates a large amount of hydrogen in the preparation process, thereby increasing the preparation cost and causing certain influence on the environment. Therefore, in order to solve the problems of high preparation cost and easy secondary pollution, domestic and foreign scholars developed a green synthesis method, and non-toxic and environment-friendly plant extract is used as a reducing agent to successfully prepare nZVI. Green synthesis ofThe method has the advantages of low cost, mild preparation conditions, low energy consumption, and nontoxic and pollution-free raw materials. However, the green synthesis method is still in experimental research stage at present, and is not really applied in practice. The carbothermic method is a method of preparing nZVI by reducing iron salts or iron oxides from carbon-based materials such as carbon black and biochar at high temperatures. The byproducts of the carbothermic method are all gases, the raw materials of carbon black and biochar are equally cheap and easy to obtain, and the preparation is easy to scale and continuous, so the carbothermic method has the characteristics of easy commercial production and the like.
However, the zero-valent iron composite material prepared at present still has the problems of small adsorption quantity, unstable material and the like.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a preparation method of a porous carbon loaded zero-valent iron composite material, so as to solve the problems that the existing zero-valent iron is high in preparation cost, difficult to realize industrial production due to the fact that the preparation process is not environment-friendly, extremely prone to spontaneous agglomeration and rapid inactivation due to oxidation in the practical use process, and the like. The porous carbon load zero-valent iron composite material with high dispersion, uniform load, large specific surface area and good stability is prepared by recycling tailings generated after rare earth is recovered from neodymium iron boron waste.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps:
(1) mixing neodymium iron boron tailings and a carbon material, sequentially adding a pore-forming agent and alcohol, and stirring to obtain a mixed primary material;
(2) and (2) sequentially carrying out ultrasonic treatment, drying and roasting on the mixed primary material obtained in the step (1) to obtain the porous carbon loaded zero-valent iron composite material.
According to the preparation method of the zero-valent iron composite material, the composite material with high lead removal performance is prepared by adopting the specific raw materials and utilizing the rare earth element neodymium in the raw materials. The prepared composite material has the characteristics of high dispersion, uniform load, large specific surface area, good stability and the like. The specific removal amount of lead can reach over 610 mg/g.
As a preferred embodiment of the present invention, the carbon material in step (1) includes 1 or a combination of at least 2 of activated carbon, carbon fiber, or carbon nanotube.
Preferably, the molar ratio of the neodymium iron boron tailings to the carbon material in the mixing in the step (1) is 1 (5-50), and may be, for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, or 1:50, but is not limited to the values listed, and other combinations not listed within this range are also applicable.
As a preferable technical scheme of the invention, the pore-forming agent in the step (1) comprises 1 or at least 2 of potassium carbonate, potassium hydroxide, potassium bicarbonate or potassium acetate.
The mass ratio of the pore-forming agent to the carbon material in step (1) is preferably 1:0.2 to 50, and may be, for example, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, although not limited thereto, and other combinations not specifically recited may be used.
As a preferred technical scheme of the invention, the alcohol in the step (1) comprises ethanol.
Preferably, the amount of the alcohol added in step (1) is 10 to 100 times the mass of the powder material, which is the mass of the tailings, the carbon material and the pore-forming agent, and may be, for example, 10 times, 20 times, 30 times, 40 times, 50 times, 60 times, 70 times, 80 times, 90 times or 100 times, but is not limited to the values listed, and other combinations not listed within this range are also applicable.
As a preferred technical solution of the present invention, the rotation speed of the stirring in step (1) is 600-800r/min, such as 600r/min, 610r/min, 620r/min, 630r/min, 640r/min, 650r/min, 660r/min, 670r/min, 680r/min, 690r/min, 700r/min, 710r/min, 720r/min, 730r/min, 740r/min, 750r/min, 760r/min, 770r/min, 780r/min, 790r/min or 800r/min, but not limited to the above values, and other combinations not listed in the range are also applicable.
Preferably, the stirring time in step (1) is 30-45min, such as 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min, but not limited to the recited values, and other combinations not recited in the range are also applicable.
As a preferred embodiment of the present invention, the power of the ultrasonic treatment in step (2) is 1100-1300W, for example, 1100W, 1110W, 1120W, 1130W, 1140W, 1150W, 1160W, 1170W, 1180W, 1190W, 1200W, 1210W, 1220W, 1230W, 1240W, 1250W, 1260W, 1270W, 1280W, 1290W, or 1300W, but is not limited to the values listed, and other combinations not listed in this range are also applicable.
Preferably, the time of the ultrasonic treatment in the step (2) is 1.5 to 2.5h, for example, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h or 2.5h, etc., but not limited to the enumerated values, and other combinations not enumerated within the range are also applicable.
As a preferred embodiment of the present invention, the drying temperature in the step (2) is 80 to 90 ℃ and may be, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃ or the like, but not limited to the values listed, and other combinations not listed in this range are also applicable.
Preferably, the drying time in step (2) is 11 to 13 hours, such as 11 hours, 11.1 hours, 11.2 hours, 11.3 hours, 11.4 hours, 11.5 hours, 11.6 hours, 11.7 hours, 11.8 hours, 11.9 hours, 12 hours, 12.1 hours, 12.2 hours, 12.3 hours, 12.4 hours, 12.5 hours, 12.6 hours, 12.7 hours, 12.8 hours, 12.9 hours or 13 hours, but not limited to the recited values, and other combinations not recited in this range are also applicable.
As a preferable embodiment of the present invention, the heating rate of the calcination in the step (2) is 10 to 15 ℃/min, and for example, 10 ℃/min, 10.5 ℃/min, 11 ℃/min, 11.5 ℃/min, 12 ℃/min, 12.5 ℃/min, 13 ℃/min, 13.5 ℃/min, 14 ℃/min, 14.5 ℃/min, or 15 ℃/min, etc., may be used, but the present invention is not limited to the above-mentioned values, and other combinations not listed in the above range are also applicable.
Preferably, the temperature for the calcination in step (2) is 500-.
As a preferable embodiment of the present invention, the heat-retaining time for the calcination in the step (2) is 1 to 3 hours, and for example, 1 hour, 1.1 hour, 1.2 hour, 1.3 hour, 1.4 hour, 1.5 hour, 1.6 hour, 1.7 hour, 1.8 hour, 1.9 hour, 2 hour, 2.1 hour, 2.2 hour, 2.3 hour, 2.4 hour, 2.5 hour, 2.6 hour, 2.7 hour, 2.8 hour, 2.9 hour or 3 hour, etc. may be mentioned, but not limited to the above-mentioned values, and other combinations not mentioned in this range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing neodymium iron boron tailings and a carbon material, sequentially adding a pore-forming agent and alcohol, and stirring to obtain a mixed primary material; the carbon material comprises 1 or a combination of at least 2 of activated carbon, carbon fiber or carbon nanotube; the molar ratio of the neodymium iron boron tailings to the carbon material in the mixing is 1 (5-50); the pore-forming agent comprises 1 or the combination of at least 2 of potassium carbonate, potassium hydroxide, potassium bicarbonate or potassium acetate; the mass ratio of the pore-forming agent to the carbon material is 1 (0.2-50); the alcohol comprises ethanol; the addition amount of the alcohol is 10-100 times of the mass of the powder; the rotating speed of the stirring is 600-800 r/min; the stirring time is 30-45 min;
(2) sequentially carrying out ultrasonic treatment, drying and roasting on the mixed primary material obtained in the step (1) to obtain the porous carbon loaded zero-valent iron composite material; the power of the ultrasonic treatment is 1100-1300W; the ultrasonic treatment time is 1.5-2.5 h; the drying temperature is 80-90 ℃; the drying time is 11-13 h; the temperature rise rate of the roasting is 10-15 ℃/min; the heat preservation temperature of the roasting is 500-1000 ℃; the roasting heat preservation time is 1-3 h.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the preparation method of the porous carbon loaded zero-valent iron composite material provided by the invention recycles the neodymium iron boron iron slag, the whole preparation process is green and environment-friendly, the cost is low, and the preparation method has very good large-scale industrial production and application potential.
(2) The porous carbon and the composite material have larger specific surface area and more pore structures, and can enhance the adsorption removal of lead; the composite material can avoid the defect that zero-valent iron is easy to agglomerate, and the activity cycle of the zero-valent iron can be prolonged by uniformly loading the zero-valent iron on the porous carbon.
(3) The rare earth element neodymium is doped in zero-valent iron to form a defect structure, which is beneficial to reducing lead ions in water by electrons generated by the zero-valent iron, thereby improving the removal rate of lead.
Drawings
FIG. 1 is an XRD pattern of a composite material obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of the composite material obtained in example 2 of the present invention;
FIG. 3 is an SEM photograph of a composite material obtained in example 2 of the present invention;
FIG. 4 shows N of the composite material obtained in example 2 of the present invention2Adsorption-removal of attached figures;
FIG. 5 is a graph showing the distribution of pore diameters of the composite material obtained in example 2 of the present invention;
FIG. 6 is an XRD pattern of the composite material obtained in example 3 of the present invention;
FIG. 7 shows N of the composite material obtained in example 3 of the present invention2Adsorption-removal of attached figures;
FIG. 8 is a spatial distribution diagram of the composite material obtained in example 3 of the present invention;
FIG. 9 is an XRD pattern of the composite material obtained in example 4 of the present invention;
FIG. 10 is an XRD pattern of the composite material obtained in example 5 of the present invention;
FIG. 11 is an SEM photograph of a composite material obtained in example 5 of the present invention;
fig. 12 is a diagram showing adsorption of lead to the composite material in application example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps:
(1) drying the neodymium iron boron iron slag at 100 ℃ for 3 hours, and naturally cooling; ball milling is carried out for 3 hours by using a ball mill;
(2) weighing 1.6g of neodymium iron boron iron slag, placing the neodymium iron boron iron slag into a beaker, and adding 1.8g of activated carbon to ensure that the neodymium iron boron iron slag (made of Fe)2O3Molar weight calculation) and activated carbon is 1:15, 5.4g of KOH is added to ensure that the mass ratio of the KOH to the activated carbon is 3:1, 100mL of absolute ethyl alcohol is added, the rotating speed of a stirrer is set to be 300r/min, and the stirring is carried out for 30 min;
(3) sealing the opening of the beaker, putting the beaker into an ultrasonic cleaning machine with the power of 1200W, and carrying out ultrasonic treatment for 2 hours at normal temperature; drying at 80 deg.C for 12 hr;
(4) and grinding the obtained dry solid, putting the ground dry solid into a crucible with a cover, and calcining the ground dry solid for 1 hour at the temperature rise rate of 10 ℃/min and the temperature of 900 ℃ to obtain the porous carbon loaded zero-valent iron composite material.
Figure 1 is the XRD pattern of the composite material prepared in example 1. As can be seen from FIG. 1, the product after reduction of the NdFeB iron tailings conforms to the characteristic peak of XRD card PDF #06-0696, which proves that the product is zero-valent iron; the potassium carbonate is generated by the reaction of potassium hydroxide and carbon.
Example 2
The embodiment provides a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps:
(1) drying the neodymium iron boron iron slag at 100 ℃ for 3 hours, and naturally cooling; ball milling is carried out for 3 hours by using a ball mill;
(2) weighing 1.6g of neodymium iron boron iron slag, placing the neodymium iron boron iron slag into a beaker, and adding 1.8g of activated carbon to ensure that the neodymium iron boron iron slag (made of Fe)2O3Molar weight ofCalculated) and the molar weight ratio of the activated carbon is 1:15, adding 1.8g of KOH to ensure that the mass ratio of the KOH to the activated carbon is 1:1, adding 100mL of absolute ethyl alcohol, setting the rotating speed of a stirrer to be 300r/min, and stirring for 30 min;
(3) sealing the opening of the beaker, putting the beaker into an ultrasonic cleaning machine with the power of 1200W, and carrying out ultrasonic treatment for 2 hours at normal temperature; drying at 80 deg.C for 12 hr;
(4) and grinding the obtained dry solid, putting the ground dry solid into a crucible with a cover, and calcining the ground dry solid for 1 hour at the temperature rise rate of 10 ℃/min and the temperature of 900 ℃ to obtain the porous carbon loaded zero-valent iron composite material.
FIG. 2 is an XRD pattern of the composite material prepared in the examples, and the characteristic peaks of zero-valent iron according to card PDF # 06-0696; FIG. 3 is an SEM image of the composite material prepared in the example, and it can be seen that the zero-valent iron in the composite material has irregular morphology but a distinct porous structure; FIG. 4 shows the adsorption-desorption diagram of composite N2 prepared in the example, and the specific surface area of the composite is 83m2(ii)/g; FIG. 5 is a graph showing the distribution of pore diameters of the composite material obtained in the example, and the average pore diameter is 2.8 nm.
Example 3
The embodiment provides a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps:
(1) drying the neodymium iron boron iron slag at 100 ℃ for 3 hours, and naturally cooling; ball milling is carried out for 3 hours by using a ball mill;
(2) weighing 1.6g of neodymium iron boron iron slag, placing the neodymium iron boron iron slag into a beaker, and adding 1.8g of activated carbon to ensure that the neodymium iron boron iron slag (made of Fe)2O3Molar weight calculation) and the molar weight ratio of the activated carbon is 1:15, 0.6g of KOH is added to ensure that the mass ratio of the KOH to the activated carbon is 1:3, 100mL of absolute ethyl alcohol is added, the rotating speed of a stirrer is set to be 300r/min, and the stirring is carried out for 30 min;
(3) sealing the opening of the beaker, putting the beaker into an ultrasonic cleaning machine with the power of 1200W, and carrying out ultrasonic treatment for 2 hours at normal temperature; drying at 80 deg.C for 12 hr;
(4) and grinding the obtained dry solid, putting the ground dry solid into a crucible with a cover, and calcining the ground dry solid for 1 hour at the temperature rise rate of 10 ℃/min and the temperature of 900 ℃ to obtain the porous carbon loaded zero-valent iron composite material.
FIG. 6 is an XRD pattern of the composite material prepared in the examples, and the characteristic peaks of zero-valent iron according to card PDF # 06-0696; FIG. 7 shows the adsorption-desorption diagram of the composite material N2 prepared in the example, wherein the specific surface area of the composite material reaches 291m2(ii)/g; FIG. 8 is a graph of the pore size distribution of the composite material prepared in the example, with an average pore size of 4.1 nm.
Example 4
The embodiment provides a preparation method of a porous carbon loaded zero-valent iron composite material, which comprises the following steps:
(1) drying the neodymium iron boron iron slag at 100 ℃ for 3 hours, and naturally cooling; ball milling is carried out for 3 hours by using a ball mill;
(2) weighing 1.6g of neodymium iron boron iron slag, placing the neodymium iron boron iron slag into a beaker, and adding 1.8g of activated carbon to ensure that the neodymium iron boron iron slag (made of Fe)2O3Molar weight calculation) and the molar weight ratio of the activated carbon is 1:15, 1.8g of KOH is added to ensure that the mass ratio of the KOH to the activated carbon is 1:1, 100mL of absolute ethyl alcohol is added, the rotating speed of a stirrer is set to be 300r/min, and the stirring is carried out for 30 min;
(3) sealing the opening of the beaker, putting the beaker into an ultrasonic cleaning machine with the power of 1200W, and carrying out ultrasonic treatment for 2 hours at normal temperature; drying at 80 deg.C for 12 hr;
(4) and grinding the obtained dry solid, putting the ground dry solid into a crucible with a cover, and calcining the ground dry solid for 1 hour at the temperature rise rate of 10 ℃/min and the temperature of 700 ℃ to obtain the porous carbon loaded zero-valent iron composite material.
FIG. 9 is the XRD pattern of the composite material prepared in the examples, and the characteristic peaks of zero-valent iron are in accordance with card PDF # 06-0696.
Example 5
The rubidium iron boron iron slag in example 4 was replaced with an equimolar amount of iron oxide powder, fig. 10 is an XRD chart of the composite material prepared in example, and fig. 11 is an SEM chart of the composite material prepared in example.
Application example 1
Experiments for removing lead in water by using the composite materials obtained in examples 1-5 are respectively marked as Sample1, Sample2, Sample3, Sample4 and Sample 5; in order to compare the lead removal effect of the composite material prepared in the example, commercial activated carbon (denoted as Sample6) and commercial reduced iron (denoted as Sample7) were selected as reference materials. In the experiment, 60mg of materials are respectively placed in a 250mL conical flask, and 150mL of lead-containing wastewater with the lead ion concentration of 20mg/L is added. Putting into a shaking table, reacting at 200r/min and room temperature (25 +/-1 ℃), sampling at 5min, 10min, 20min, 30min and 60min respectively, and determining the lead concentration in the solution after the reaction. The adsorption results are shown in detail in FIG. 12.
As can be seen from the results in fig. 12, compared with the composite material in the prior art, the composite material obtained in the present invention contains a rare earth element introduced with neodymium, and neodymium is doped in zero-valent iron to form a defect structure, which is helpful for reducing lead ions in a water body by electrons generated by the zero-valent iron, thereby improving the removal rate of lead.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The preparation method of the porous carbon loaded zero-valent iron composite material is characterized by comprising the following steps:
(1) mixing neodymium iron boron tailings and a carbon material, sequentially adding a pore-forming agent and alcohol, and stirring to obtain a mixed primary material;
(2) and (2) sequentially carrying out ultrasonic treatment, drying and roasting on the mixed primary material obtained in the step (1) to obtain the porous carbon loaded zero-valent iron composite material.
2. The method according to claim 1, wherein the carbon material of step (1) comprises 1 or a combination of at least 2 of activated carbon, carbon fiber, or carbon nanotube;
preferably, the molar ratio of the neodymium iron boron tailings to the carbon material in the mixing in the step (1) is 1 (5-50).
3. The method of claim 1 or 2, wherein the pore-forming agent of step (1) comprises 1 or a combination of at least 2 of potassium carbonate, potassium hydroxide, potassium bicarbonate, or potassium acetate;
preferably, the mass ratio of the pore-forming agent to the carbon material in the step (1) is 1 (0.2-50).
4. The method according to any one of claims 1 to 3, wherein the alcohol of step (1) comprises ethanol;
preferably, the adding amount of the alcohol in the step (1) is 10-100 times of the mass of the powder.
5. The method according to any one of claims 1-4, wherein the rotation speed of the stirring in step (1) is 600-800 r/min;
preferably, the stirring time of the step (1) is 30-45 min.
6. The method according to any one of claims 1 to 5, wherein the power of the ultrasonic treatment in the step (2) is 1100-;
preferably, the time of the ultrasonic treatment in the step (2) is 1.5-2.5 h.
7. The method according to any one of claims 1 to 6, wherein the drying temperature in the step (2) is 80 to 90 ℃;
preferably, the drying time in the step (2) is 11-13 h.
8. The production method according to any one of claims 1 to 7, wherein the temperature increase rate of the calcination in the step (2) is 10 to 15 ℃/min;
preferably, the temperature for the calcination in the step (2) is 500-1000 ℃.
9. The method according to any one of claims 1 to 8, wherein the calcination in the step (2) is carried out for a holding time of 1 to 3 hours.
10. The method of any one of claims 1 to 9, comprising the steps of:
(1) mixing neodymium iron boron tailings and a carbon material, sequentially adding a pore-forming agent and alcohol, and stirring to obtain a mixed primary material; the carbon material comprises activated carbon; the molar ratio of the neodymium iron boron tailings to the carbon material in the mixing is 1 (5-50); the pore-forming agent comprises 1 or the combination of at least 2 of potassium carbonate, potassium hydroxide, potassium bicarbonate or potassium acetate; the mass ratio of the pore-forming agent to the carbon material is 1 (0.2-50); the alcohol comprises ethanol; the addition amount of the alcohol is 10-100 times of the mass of the powder; the rotating speed of the stirring is 600-800 r/min; the stirring time is 30-45 min;
(2) sequentially carrying out ultrasonic treatment, drying and roasting on the mixed primary material obtained in the step (1) to obtain the porous carbon loaded zero-valent iron composite material; the power of the ultrasonic treatment is 1100-1300W; the ultrasonic treatment time is 1.5-2.5 h; the drying temperature is 80-90 ℃; the drying time is 11-13 h; the temperature rise rate of the roasting is 10-15 ℃/min; the heat preservation temperature of the roasting is 500-1000 ℃; the roasting heat preservation time is 1-3 h.
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| CN116251596A (en) * | 2021-12-01 | 2023-06-13 | 中国科学院江西稀土研究院 | Composite material and preparation method and application thereof |
| CN118263018A (en) * | 2024-02-23 | 2024-06-28 | 中国矿业大学 | Method for preparing micro-nano magnetic composite material from neodymium-iron-boron secondary waste and application |
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Address after: 341000 No. 1, chutanwei Academy of Sciences Road, Chutan Town, Ganxian District, Ganzhou City, Jiangxi Province Applicant after: Jiangxi Rare Earth Research Institute Chinese Academy of Sciences Address before: 341003 No.36, Huangjin Avenue, Ganzhou economic and Technological Development Zone, Ganzhou City, Jiangxi Province Applicant before: Jiangxi Rare Earth Research Institute Chinese Academy of Sciences |
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Application publication date: 20211102 |