CN110668557A - Preparation method and application of carbon-based zero-valent iron material - Google Patents
Preparation method and application of carbon-based zero-valent iron material Download PDFInfo
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- CN110668557A CN110668557A CN201911003800.8A CN201911003800A CN110668557A CN 110668557 A CN110668557 A CN 110668557A CN 201911003800 A CN201911003800 A CN 201911003800A CN 110668557 A CN110668557 A CN 110668557A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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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
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Abstract
The invention discloses a preparation method and application of a carbon-based zero-valent iron material. The carbon-based zero-valent iron material comprises a carrier and a load, wherein the carrier is melamine foam carbon or polyurethane foam carbon, and the load is zero-valent iron. The preparation method of the material comprises the following steps: 1) carbonizing melamine foam or polyurethane foam to obtain foam carbon; 2) the foam carbon is dipped in the ferric salt solution and then subjected to reduction reaction to obtain the product. Also discloses the application of the material in sewage denitrification. The invention adopts commercial foam plastic as a precursor to prepare the foam carbon material through high-temperature carbonization, and the carbon material is used as a load material of zero-valent iron. The material has a spatial three-dimensional structure, is ultra-light in weight, high in porosity and good in electron conductivity, is beneficial to zero-valent iron attachment, is beneficial to electron conduction in a reaction process, is high in treatment efficiency in a water treatment process, can be used as a biological reaction tank filler, and fully utilizes the advantages of zero-valent iron and biological water treatment.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method and application of a carbon-based zero-valent iron material.
Background
Nitrate nitrogen pollution is one of the most serious environmental pollution problems in the world. In the current mainstream wastewater treatment process, the removal of nitrate nitrogen mainly depends on the metabolism of microorganisms of the denitrification process, from nitrate nitrogen to N2The conversion process of (a) consists of a series of electron transfer steps, requiring an electron donor to maintain denitrification efficiency.
Low negativity of zero-valent ferroelectrics and strong reducing power
Low price, rich source and good environmental compatibility, and has attracted extensive attention in the aspects of degrading and removing organic and inorganic pollutants in the environment. As early as the early nineties, developed countries in Europe and America have been restoring groundwater by establishing permeable reactive walls with zero-valent iron as filler, and the application stage has been reached. However, this reaction removes nitrate nitrogen, but its nitrogen-containing product ammonium nitrogen is also a contaminant, deviating from the intended goal of water treatment. For the reaction of zero-valent iron with nitrate, the more thermodynamically favored product is N2And is a desirable end product which is environment-friendly and can be directly discharged without secondary treatment.
The existing preparation method of zero-valent iron comprises high-temperature reduction, ball milling and sodium borohydride wet reduction, and the load materials generally comprise minerals such as ceramic balls, diatomite and the like, activated carbon, biological carbon and the like. Some researchers tried to reduce or avoid NH by means of modification of zero-valent iron, optimization of reaction conditions, mixing with materials such as zeolite and activated carbon4 +Among the most promising engineering applications is the coupling of zero-valent iron with microorganisms. The zero-valent iron can be used as an electron donor for biological denitrification, so that an external carbon source is avoided; biological denitrification can be directed to the conversion of nitrate nitrogen into nitrogen. The combination of the two can get rid of the dependence of biological denitrification on carbon source, and inhibit the independent reduction of nitrate by zero-valent ironThe generation of ammonia nitrogen in the nitrogen process is expected to realize the effective nitrate nitrogen directional transformation.
The existing zero-valent iron-loaded biological filler mainly comprises two types, wherein one type is zero-valent iron loaded polymer, and the polymer provides large specific surface area and porous performance. However, the polymer is generally an insulator and is not conductive, cannot transmit electrons, does not participate in biological and chemical reactions in the water treatment process, and is only used as a supporting material. The other is biological carbon loaded with zero-valent iron, the carbon material has electron conduction performance and can play an electron transfer role in biological and chemical reaction processes, but the biological carbon is not easy to collect and prepare on a large scale, the pore diameter morphology is not easy to control, and the performance difference of different batches is large.
Disclosure of Invention
In order to overcome the problems of zero-valent iron sewage treatment materials in the prior art, the invention aims to provide a carbon-based zero-valent iron material, the invention aims to provide a preparation method of the carbon-based zero-valent iron material, and the invention aims to provide application of the carbon-based zero-valent iron material.
The invention concept of the invention is as follows: the method utilizes commercial foam plastics as a precursor to prepare the three-dimensional foam carbon material, and then utilizes chemical reduction to load zero-valent iron on foam carbon, so that the prepared zero-valent iron/foam carbon material can be independently used in a sewage denitrification process and can also be used as a biological denitrification treatment filler.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a carbon-based zero-valent iron material. The carbon-based zero-valent iron material comprises a carrier and a load; wherein, the carrier is melamine foam carbon or polyurethane foam carbon; the load is zero-valent iron.
Preferably, in the carbon-based zero-valent iron material, the load capacity of the load is 5-50% of the mass of the carrier; more preferably, the loading amount of the load is 8% to 15% of the mass of the carrier.
The invention provides a preparation method of the carbon-based zero-valent iron material.
A preparation method of a carbon-based zero-valent iron material comprises the following steps:
1) carbonizing melamine foam or polyurethane foam to obtain foam carbon;
2) and (3) soaking the carbon foam into an iron salt solution, and then carrying out reduction reaction on the carbon foam material soaked with the iron salt to obtain the carbon-based zero-valent iron material.
In step 1) of the preparation method of the carbon-based zero-valent iron material, the melamine foam or the polyurethane foam are both polymer materials containing amine repeating units. The melamine foam or polyurethane foam used in the present invention is a commercial foam, and is commercially available from a conventional commercial source. Preferably, melamine foam is selected in step 1).
Preferably, in step 1) of the preparation method of the carbon-based zero-valent iron material, the reaction conditions of carbonization are as follows: the heating rate (the rate of heating from room temperature to the final carbonization temperature) is 3-6 ℃/min; the final carbonization temperature is 500-1000 ℃; the maintaining time at the final carbonization temperature is 0.5 h-3 h; carbonizing in an oxygen-free atmosphere; further preferably, the temperature rise rate of carbonization is 5 ℃/min; the final carbonization temperature is 850-950 ℃; the maintaining time at the final carbonization temperature is 0.8 h-1.2 h; the oxygen-free atmosphere is inert gas or nitrogen atmosphere.
Preferably, in step 2) of the preparation method of the carbon-based zero-valent iron material, the foamy carbon is dipped into the iron salt solution, specifically, the foamy carbon and the iron salt solution are mixed and shaken; the shaking is carried out for 3 to 6 hours at the speed of 150 to 200r/min in a shaking table; shaking is carried out at room temperature, such as 20-25 ℃.
In the step 2) of the preparation method of the carbon-based zero-valent iron material, the iron salt of the iron salt solution is ferric salt or ferrous salt. Preferably, the iron salt of the iron salt solution is selected from iron chloride (FeCl)3) Iron (Fe) sulfate2(SO4)3) Iron nitrate (Fe (NO)3)3) Ferrous chloride (FeCl)2) Ferrous sulfate (FeSO)4) Ferrous nitrate (Fe (NO)3)2) At least one of (1). These iron salts may be hydrated or non-hydrated salts. In some preferred embodiments, the iron salt is a chlorideIron.
Preferably, in the step 2) of the preparation method of the carbon-based zero-valent iron material, the concentration of the iron salt in the iron salt solution is 0.1-0.5 mol/L; more preferably, the iron salt concentration of the iron salt solution is 0.15mol/L to 0.25 mol/L.
Preferably, in step 2) of the preparation method of the carbon-based zero-valent iron material, the mass ratio of the foam carbon to the Fe in the iron salt is 1: (20-100); further preferably, the mass ratio of the carbon foam to the Fe in the iron salt is 1: (30-50).
Preferably, in step 2) of the preparation method of the carbon-based zero-valent iron material, the dosage ratio of the foam carbon to the iron salt solution is 1 g: (2-5) L; further preferably, the dosage ratio of the foam carbon to the ferric salt solution is 1 g: (3-4) L.
Preferably, in step 2) of the preparation method of the carbon-based zero-valent iron material, the reduction reaction is a heating reduction reaction or a borohydride wet reduction reaction.
When the reduction reaction in the step 2) is a heating reduction reaction, the heating reduction reaction is specifically: heating the foamy carbon material soaked with the ferric salt solution to 300-500 ℃ in an oxygen-free atmosphere, and reacting for 1-3 h; preferably, the oxygen-free atmosphere is an inert gas or nitrogen atmosphere; the heating temperature is 330-370 ℃; the reaction time is 1.5 h-2.5 h.
Preferably, the method further comprises the step of drying the foamy carbon material impregnated with the iron salt solution before the heating reduction reaction; the preferred manner of drying is to blow dry the foamy carbon material after impregnation with the iron salt solution with nitrogen.
When the reduction reaction in the step 2) is a borohydride wet reduction reaction, the borohydride wet reduction reaction is specifically: and mixing the foamy carbon material soaked with the ferric salt solution with a borohydride solution for reaction.
Preferably, in the borohydride wet reduction reaction, the mixing reaction time is 20min to 60 min; most preferably, the time of the borohydride wet reduction reaction is 30 min.
Preferably, in the borohydride wet reduction reaction, the borohydride is selected from sodium borohydride (NaBH)4) Potassium borohydride (KBH)4) At least one of (1).
Preferably, in the borohydride wet reduction reaction, the borohydride concentration of the borohydride solution is 1 mol/L-1.5 mol/L; further preferably, the concentration of borohydride in the borohydride solution is 1.1mol/L to 1.3 mol/L.
Preferably, in the borohydride wet reduction reaction, the molar ratio of Fe in the iron salt to borohydride in the borohydride solution is 1: (5-7); most preferably, the molar ratio of Fe in the iron salt to borohydride in the borohydride solution is 1: 6.
preferably, after the borohydride wet reduction reaction, the method further comprises the steps of washing and drying the product; preferably, after the borohydride wet reduction reaction, the product is washed by water and ethanol in sequence, then is blown by nitrogen for 20-40 min, and then is dried in a vacuum drying oven at 50-70 ℃ for 10-15 h; still more preferably, after the borohydride wet reduction reaction, the product is washed by oxygen-free water and absolute ethyl alcohol in sequence, then is blown by nitrogen for 30min, and then is dried in a vacuum drying oven at 60 ℃ for 12 h. And washing and drying to obtain the final carbon-based zero-valent iron product.
In the preparation method of the carbon-based zero-valent iron material, the ferric salt solution and the borohydride solution are respectively aqueous solutions.
The invention also provides application of the carbon-based zero-valent iron material. In particular to the application of the carbon-based zero-valent iron material in sewage denitrification.
Preferably, in the application, the carbon-based zero-valent iron material can be used as a biological denitrification treatment filler and is combined with a biological method to be used in a water denitrification treatment process; or the carbon-based zero-valent iron material is directly and independently used for the water denitrification treatment process. When the carbon-based zero-valent iron material is directly used for sewage denitrification treatment, the carbon-based zero-valent iron material is mixed with sewage for denitrification treatment. The sewage is sewage containing nitrate nitrogen.
The invention has the beneficial effects that:
the invention adopts commercial foam plastic as a precursor to prepare the foam carbon material through high-temperature carbonization, and the carbon material is used as a load material of zero-valent iron. The material has a spatial three-dimensional structure, is ultra-light in weight, high in porosity and good in electron conductivity, is beneficial to zero-valent iron attachment, is beneficial to electron conduction in the reaction process, and is high in treatment efficiency in the water treatment process. Meanwhile, the biological reaction tank can be attached with growing microorganisms, can be used as a biological reaction tank filler, and fully utilizes the advantages of zero-valent iron and biological water treatment.
Specifically, the three-dimensional carbon foam material is prepared by taking melamine foam as a precursor, is a good electronic conductor, has a regular structure and a large porosity, is not easy to block, and can be uniformly loaded with zero-valent iron. Meanwhile, the three-dimensional foamy carbon material prepared by taking the melamine foam as the precursor contains abundant N-C bonds, which is beneficial to electron transfer and microbial growth. The material can be stably prepared in a large scale, is easy to mold, and can easily obtain the filter material filler suitable for actual shape requirements.
Drawings
FIG. 1 is a schematic flow diagram of an example process for preparing a carbon-based zero-valent iron material;
FIG. 2 is a schematic illustration of a melamine foam sponge and carbon foam;
FIG. 3 is a scanning electron micrograph of a melamine foam sponge;
FIG. 4 is a scanning electron micrograph of carbon foam at 830 times magnification;
FIG. 5 is a scanning electron micrograph of carbon foam at 3700 times magnification;
FIG. 6 is a scanning electron microscope image of carbon-based zero-valent iron material at 890 times magnification;
FIG. 7 is a scanning electron microscope image of a carbon-based zero-valent iron material magnified 4900 times;
fig. 8 is a graph of nitrate nitrogen removal efficiency.
Detailed Description
The process schematic diagram for preparing the carbon-based zero-valent iron material in the embodiment of the invention is shown in the attached figure 1. The present invention will be described in further detail with reference to fig. 1 by way of specific examples.
The starting materials, reagents or apparatus used in the examples were obtained from conventional commercial sources unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Examples of production of foamed carbon Material
The preparation method of the foamy carbon material comprises the following steps:
placing a melamine foam sponge with the size of 2cm multiplied by 1cm in N2Heating to 900 ℃ at the heating rate of 5 ℃/min in the atmosphere, and calcining for 1h at 900 ℃. After carbonization, a black melamine carbon skeleton with the size of 1cm multiplied by 0.4cm, namely the foamy carbon material, is obtained. Figure 2 shows a schematic representation of a melamine foam sponge and carbon foam.
The scanning electron microscope image of the melamine foam sponge is shown in the attached figure 3. Scanning electron micrographs of carbon foam prepared from this melamine foam sponge at 830 and 3700 magnifications are shown in FIGS. 4 and 5, respectively.
Preparation of carbon-based zero-valent iron Material example 1
The preparation method of the carbon-based zero-valent iron material comprises the following steps:
50mL of 0.2mol/L FeCl is taken3Putting the solution into a conical flask, adding 0.014g of foam carbon, sealing, and placing in a shaking table at 180r/min and 20 ℃ for 3 h; the excess liquid was decanted off and 50mL of 1.2mol/L NaBH was added using a peristaltic pump4And (3) placing the solution in a conical flask, standing for 0.5h, washing with oxygen-free water for a plurality of times, washing with absolute ethyl alcohol for 3 times, blowing with nitrogen for 0.5h, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain the zero-valent iron/foamy carbon material.
Preparation example 2 of carbon-based zero-valent iron Material
The preparation method of the carbon-based zero-valent iron material comprises the following steps:
50mL of 0.2mol/L FeCl is taken3Putting the solution into a conical flask, adding 0.014g of foam carbon, sealing, and placing in a shaking table at 180r/min and 20 ℃ for 3 h; pouring out the redundant liquid, and drying the material by using nitrogen; and then putting the material into a high-temperature tubular furnace, heating the material from room temperature to 350 ℃ in a nitrogen atmosphere, reacting for 2 hours, cooling the material to room temperature, and taking the material out to obtain the zero-valent iron/foamed carbon material.
The scanning electron micrographs of the carbon-based zero-valent iron material of the embodiment magnified 890 times and 4900 times are respectively shown in FIG. 6 and FIG. 7. After detection, the product is prepared by the exampleThe density of the zero-valent iron/foamed carbon material is 0.007g/cm3BET specific surface area of 725.82m2The loading of zero-valent iron is 10 wt% of the foam carbon.
Application example
Potassium nitrate solution was prepared for application test. Under the conditions that the solution is neutral in pH and the initial nitrate concentration is 50mg/L, equimolar amounts (0.02mol/L) of common commercial nano zero-valent iron and the carbon-based zero-valent iron material prepared in example 2 are added respectively for denitrification experiments. The test results for nitrate removal are shown in FIG. 8.
As can be seen from FIG. 8, the zero-valent iron/foamy carbon material obtained in the example can completely remove 100mg/L of nitrate nitrogen within 2 hours, and the denitrification efficiency is obviously higher than that of the common commercial nano zero-valent iron material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, 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 thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A carbon-based zero-valent iron material is characterized in that: comprises a carrier and a load; the carrier is melamine foam carbon or polyurethane foam carbon; the load is zero-valent iron.
2. The carbon-based zero-valent iron material of claim 1, wherein: the loading capacity of the load is 5-50% of the mass of the carrier.
3. A method for preparing the carbon-based zero-valent iron material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
1) carbonizing melamine foam or polyurethane foam to obtain foam carbon;
2) and (3) soaking the carbon foam into an iron salt solution, and then carrying out reduction reaction on the carbon foam material soaked with the iron salt to obtain the carbon-based zero-valent iron material.
4. The production method according to claim 3, characterized in that: in the step 1), the reaction conditions of carbonization are as follows: the heating rate is 3 ℃/min to 6 ℃/min; the final carbonization temperature is 500-1000 ℃; the maintaining time at the final carbonization temperature is 0.5 h-3 h; the carbonization is carried out in an oxygen-free atmosphere.
5. The production method according to claim 3, characterized in that: in the step 2), the ferric salt of the ferric salt solution is selected from at least one of ferric chloride, ferric sulfate, ferric nitrate, ferrous chloride, ferrous sulfate and ferrous nitrate.
6. The method of claim 5, wherein: in the step 2), the concentration of the ferric salt in the ferric salt solution is 0.1-0.5 mol/L.
7. The method of claim 6, wherein: in the step 2), the mass ratio of the carbon foam to Fe in the ferric salt is 1: (20-100).
8. The production method according to claim 3, characterized in that: in the step 2), the reduction reaction is a heating reduction reaction or a borohydride wet reduction reaction.
9. Use of the carbon-based zero-valent iron material of claim 1 or 2 in denitrification of wastewater.
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| CN111620318A (en) * | 2020-06-08 | 2020-09-04 | 东北农业大学 | Preparation method of nano zero-valent iron particle-loaded foam carbon composite material |
| CN111871443A (en) * | 2020-08-11 | 2020-11-03 | 电子科技大学 | Preparation method and application of melamine foam-based nanocomposite |
| CN112830575A (en) * | 2020-12-31 | 2021-05-25 | 北京工业大学 | Preparation method, product and application of substrate sludge-based biochar-loaded nano zero-valent iron immobilized denitrifying bacteria active microspheres |
| CN113000022A (en) * | 2021-03-02 | 2021-06-22 | 中国地质大学（武汉） | Manganese-doped nano lepidocrocite/carbon foam composite material, preparation method and application |
| CN115403162A (en) * | 2022-08-03 | 2022-11-29 | 中国石油化工股份有限公司 | Foam carbon-based zero-valent iron material, preparation method thereof and application thereof in permeable reactive barrier |
| CN115739178A (en) * | 2022-09-08 | 2023-03-07 | 河北科技大学 | Preparation method and application of phenolic foam loaded manganese ferrite catalyst |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620318A (en) * | 2020-06-08 | 2020-09-04 | 东北农业大学 | Preparation method of nano zero-valent iron particle-loaded foam carbon composite material |
| CN111620318B (en) * | 2020-06-08 | 2023-04-25 | 东北农业大学 | Preparation method of nano zero-valent iron particle loaded foam carbon composite material |
| CN111871443A (en) * | 2020-08-11 | 2020-11-03 | 电子科技大学 | Preparation method and application of melamine foam-based nanocomposite |
| CN112830575A (en) * | 2020-12-31 | 2021-05-25 | 北京工业大学 | Preparation method, product and application of substrate sludge-based biochar-loaded nano zero-valent iron immobilized denitrifying bacteria active microspheres |
| CN113000022A (en) * | 2021-03-02 | 2021-06-22 | 中国地质大学（武汉） | Manganese-doped nano lepidocrocite/carbon foam composite material, preparation method and application |
| CN113000022B (en) * | 2021-03-02 | 2022-03-22 | 中国地质大学（武汉） | Manganese-doped nano lepidocrocite/carbon foam composite material, preparation method and application |
| CN115403162A (en) * | 2022-08-03 | 2022-11-29 | 中国石油化工股份有限公司 | Foam carbon-based zero-valent iron material, preparation method thereof and application thereof in permeable reactive barrier |
| CN115739178A (en) * | 2022-09-08 | 2023-03-07 | 河北科技大学 | Preparation method and application of phenolic foam loaded manganese ferrite catalyst |
| CN115739178B (en) * | 2022-09-08 | 2024-03-26 | 河北科技大学 | Preparation method and application of phenolic foam supported manganese ferrite catalyst |
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Application publication date: 20200110 |