CN111097414B - Simple method for loading superfine nano zero-valent iron on porous material - Google Patents
Simple method for loading superfine nano zero-valent iron on porous material Download PDFInfo
- Publication number
- CN111097414B CN111097414B CN201911268721.XA CN201911268721A CN111097414B CN 111097414 B CN111097414 B CN 111097414B CN 201911268721 A CN201911268721 A CN 201911268721A CN 111097414 B CN111097414 B CN 111097414B
- Authority
- CN
- China
- Prior art keywords
- valent iron
- zero
- porous material
- iron
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to the technical field of high-toxicity pollutant treatment, and relates to a simple and convenient method for loading superfine nano zero-valent iron on a porous material and application of the method as an adsorbent and a heterogeneous Fenton catalyst to degrade and remove pollutants. The organic ferric salt, the organic ligand and the porous material only need to be simply mixed and then carbonized at high temperature under the protection of inert gas, and the superfine zero-valent iron can be uniformly loaded on the inner and outer surfaces and pore channels of the porous material. The method omits a complex, time-consuming and harsh liquid-phase impregnation process in a conventional liquid-phase reduction method, does not need any solvent or dispersant, and has high utilization rate of raw materials. The obtained zero-valent iron has large loading capacity, good crystallinity and small particle size. The porous material loaded with the superfine nano zero-valent iron can be used as an adsorbent and a catalyst, and high-toxicity inorganic and organic pollutants in water are removed by utilizing adsorption, Fe-C micro-electrolysis technology and Fenton oxidation technology.
Description
Technical Field
The invention belongs to the technical field of high-toxicity pollutant treatment, and relates to a simple and convenient method for loading superfine nano zero-valent iron on a porous material and application of the method as an adsorbent and a heterogeneous Fenton catalyst to degrade and remove pollutants.
Background
Iron is the most abundant transition metal and fourth most abundant element on the earth's surface. Accordingly, iron-based materials are receiving increasing attention in various environmental engineering fields. Strong reduction of zero-valent ironImmunogenicity (E)0-0.44V) and good adsorption capacity for important pollutants (such as heavy metals and metal colloids) have led to their widespread use in environmental remediation research. The earliest environmental application of nano zero-valent iron (nZVI) was reductive dechlorination in chlorine-containing solvents. The nano zero-valent iron material has stronger activity than the traditional iron powder or iron filling material, so the nano zero-valent iron has unique application potential in the aspect of in-situ remediation of polluted soil and underground water. Due to the large area/volume ratio, magnetic properties and surface energy and activity, nano ZVI is highly susceptible to agglomeration into micron or millimeter sized particles. In addition, nZVI can also react with dissolved oxygen and water, thereby deactivating it. Mondal et al reported that the actual size of nano-sized nZVI in water was 17.7 μm due to agglomeration of nZVI. For this reason, many researchers have solved the problem of easy agglomeration by loading nano-iron onto porous carriers such as biomass carbon, inorganic minerals, etc. The nano zero-valent iron is loaded on the porous substance, so that the inherent characteristics of the porous substance can be maintained, the stability can be enhanced, the oxidation rate of the nano zero-valent iron is reduced, the agglomeration of particles is relieved, the degradation efficiency is improved, and the particles can be recycled.
At present, the loading method of the nano zero-valent iron mainly comprises the following 3 methods: electrochemical deposition, liquid phase reduction and carbothermic processes. The electrochemical deposition method is to deposit reduced zero-valent iron on the electrode under the action of an electric field, and the prepared nanocrystal material has high density, small gap and less limitation of size and shape. The liquid phase reduction method is that firstly the iron compound is loaded on the carrier by adsorption or deposition, etc., then the iron salt is reduced to zero-valent iron by strong reducing agent solution, and said method mainly uses NaBH4Is a reducing agent. The prepared nano zero-valent iron has high activity, but the price of the reducing agent is higher, and a large amount of hydrogen generated in the synthesis process hinders the large-scale production of the reducing agent, and in order to ensure the reduction process, N is generally introduced2Aeration or vacuum operation also increases the operating cost. When the carrier is a material with stronger hydrophobicity such as activated carbon, the soaking solvent usually contains organic components, such as ethanol, so as to increase the wettability of the material; in order to make iron ions enter the inner surface of the micropores of the activated carbon, a dispersing agent such as polyethylene glycol needs to be added into the solution, so that the operation cost is further increased. Although the activity of the nano zero-valent iron loaded by the liquid phase reduction method is high, the iron is easily corroded by dissolved oxygen or water, so that the activity is quickly lost, a large amount of red mud is generated, and the subsequent treatment cost is increased.
The carbothermic process is a redox reaction carried out at high temperature using inorganic carbon as a reducing agent. The carbothermic method has the advantages that the by-product in the generation process is gas, the reaction process is an endothermic process, and the production is easy to scale and continuous. The production process has a high-temperature sintering process, the combination degree of the nano zero-valent iron and the material is high, and the nano zero-valent iron is not easy to fall off. In the high-temperature heating process, inorganic carbon is easy to deposit on the surface of zero-valent iron, and a core-shell type zero-valent iron @ carbon composite material is generated. The composite material can avoid direct contact of zero-valent iron and substances such as oxygen, water and the like, thereby relieving corrosion and inactivation of the composite material in water. Therefore, the carbothermic method is a preparation method with great prospect. For example, Hoch and the like use reactive iron salt as a raw material, and adsorb or immerse iron to a specific surface area of 80m in an argon environment at a high temperature of 600-800 DEG C2In the carbon black per gram, the obtained composite material has the characteristic of good fluidity. The polymer has a particle size of about 20-150 nm of nZVI, and the flake carbon black has a diameter of 20nm and a specific surface area of 30-130 m2(ii) in terms of/g. When the carbothermic method is adopted to carry zero-valent iron on the porous material, the liquid phase impregnation method is usually needed to firstly adsorb iron ions on the inner surface and the outer surface of the porous material. In order to prevent hydrolysis of iron ions, organic dispersant (such as polyethylene glycol) is also required to be added in the impregnation process, and N is introduced2Aeration or vacuum operation, adds complexity to the operation. Therefore, in order to simplify the method of supporting zero-valent iron, increase the amount of zero-valent iron supported, and reduce the particle size of zero-valent iron, it is necessary to develop a new method of simply and highly supporting zero-valent nano-iron.
The relevant documents can be referred to:
[1]R.Singh,V.Misra,R.P.Singh,Remediation ofγ-Hexachlorocyclohexane contaminated soil using nanoscale zero-valent iron.J.Bionanosci.,2011,5(1),82–87.
[2]M.Zhang,F.He,D.Zhao,X.Hao,Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles:effects of sorption,surfactants,and natural organic matter.Water Res.,2011,45(7),2401-2414.
[3]K.Mondal,G.Jegadeesan,S.B.Lalvani,Removal of selenate by Fe and NiFe nanosized particles.Ind.Eng.Chem.Res.,2004,43(16),4922-4934.
[4]Y.F.Su,Y.L.Cheng,Y.Shih,Removal of trichloroethylene by zero valent iron/activated carbon derived from agricultural wastes.Environ.Manage.2013,129,361-366.
[5]B.Sunkara,J.Zhan,J.He,G.L.McPherson,G.Piringer,V.T.John,Nanoscale zerovalent iron supported on uniform carbon microspheres for the in situ remediation of chlorinated hydrocarbons.ACS Appl.Mater.Inter.2010,2(10),2854-2862.
[6]L.B.Hoch,E.J.Mack,B.W.Hydutsky,J.M.Hershman,J.M.Skluzacek,T.E.Mallouk,Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium.Environ.Sci.Technol.2008,42(7),2600-2605.
[7]J.Sun,L.Zhang,C.Ge,C.Tang,L.Dong,Comparative study on the catalytic CO oxidation properties of CuO/CeO2 catalysts prepared by solid state and wet impregnation.Chinese J.Catal.2014,35,1347–1358.
[8]Y.Dai,Y.Hu,B.Jiang,J.Zou,G.Tian,H.Fu,Carbothermal synthesis of ordered mesoporous carbon-supported nano zero-valent iron with enhanced stability and activity for hexavalent chromium reduction.J.Hazard.Mater.2016,309,249–258.
[9]S.S.Park,S.-W.Chu,C.Xue,D.Zhao,C.-S.Ha,Facile synthesis of mesoporous carbon nitrides using the incipient wetness method and the application as hydrogen adsorbent.J.Mater.Chem.2011,21,10801-10807.
[10]X.Liu,D.Lai,Y,Wang,Performance of Pb(II)removal by an activated carbon supported nanoscale zero-valent iron composite at ultralow iron content.J.Hazard.Mater.2019,361,37–48.
disclosure of Invention
The invention aims to provide a method for simply and conveniently loading superfine nano zero-valent iron on a porous material and taking the porous material as an adsorbent and a heterogeneous Fenton catalyst to efficiently degrade and remove pollutants.
The invention also aims to provide a preparation method of the porous material loaded with the nano zero-valent.
The purpose of the invention is realized by adopting the following technical scheme.
In one aspect, the invention provides a catalyst of a porous material loaded with superfine nano zero-valent iron, and the material is prepared from porous materials such as coke, montmorillonite, attapulgite, activated carbon and core-shell nano zero-valent iron (Fe)0) Or iron carbide (Fe)3C) Carbon material composition. For powdered clay minerals, activated carbon, etc., these core-shell type zero-valent iron @ carbon have a diameter of between 2 and 5 nm; for the coke in bulk, the core-shell type zero-valent iron @ carbon has a diameter of between 40 and 500nm (smaller particle size zero-valent iron @ carbon composites cannot be observed by scanning electron microscopy). The core-shell type zero-valent iron @ carbon is uniformly dispersed on the inner surface and the outer surface of the porous material. The loading capacity of the zero-valent iron can be conveniently adjusted according to the proportion of the added iron source.
On the other hand, the invention provides a preparation method of the porous material adsorbent and the catalyst loaded with the superfine nano zero-valent iron, which comprises the following steps: (1) weighing a certain proportion of organic ferric salt and organic ligand and mixing with the porous substance; (2) and (2) adding the mixed solid obtained in the step (1) into a crucible, and heating at the high temperature of 700-.
In a preferred embodiment of the present invention, the organic iron salt is selected from ferrous acetate, ferrous citrate, ferric acetylacetonate, etc., preferably ferrous acetate.
In a preferred embodiment of the present invention, the organic ligand is selected from the group consisting of terephthalic acid, 2-amino terephthalic acid, EDTA, dopamine, chitosan, etc., preferably EDTA.
In a preferred embodiment of the present invention, the porous material is selected from coke, montmorillonite, attapulgite, activated carbon, and the like.
In a preferred embodiment of the present invention, the mass ratio of the organic iron salt to the organic ligand is 5:1 to 1: 1.
In a preferred embodiment of the invention, the ratio of the powdered porous material and the organic iron salt is from 8:1 to 100:1(g: g); the ratio of the blocky porous material to the organic iron salt is 37.5:1-150: 1.
In a preferred embodiment of the present invention, the high temperature carbonization heating temperature is 700-1000 ℃, and the reaction time is 1-4 hours.
In another aspect, the porous material adsorbent and the catalyst loaded with the superfine nano zero-valent iron provided by the invention are preferably selected from a highly toxic and difficultly degradable organic dye methyl orange in the application of removing pollutants in an environmental water sample.
Therefore, the method for loading the superfine nano zero-valent iron on the porous material is simple, and no solvent or dispersant is needed; the preparation time of the material is greatly shortened due to the omission of a time-consuming liquid phase impregnation process. In the material heating process, iron ions in the uniformly mixed organic iron salt and an organic ligand generate chelation, and monatomic iron or zero-valent iron nanoclusters are generated under the condition of high-temperature inert gas; because the particles are fine, the product is similar to gas, and can enter the pore canal and the inner surface of the porous material, so that the zero-valent iron nano-particles are uniformly distributed on the inner surface, the outer surface and the pore canal of the porous material. We call this method "fumigation". The particle size and loading of the zero-valent iron can be conveniently adjusted by varying the proportions of the iron source, organic ligand and porous material. The loading of the nano zero-valent iron increases the surface area and the adsorption/catalysis sites of the porous material, and is beneficial to enhancing the pollutant removal capacity of the composite material. The iron source of the fumigation method provided by the invention has high utilization rate. Taking coke as an example, when the ratio of the iron source to the coke is 0.2:45, 0.3:45, 0.6:45 and 0.9:45 respectively, the theoretical loading of zero-valent iron is 1.3 per thousand, 2.0 per thousand, 4.0 per thousand and 6.0 per thousand, the actually detected loading is 0.7 per thousand, 1.1 per thousand, 1.9 per thousand and 2.7 per thousand respectively, and the utilization rate of the raw material is 50%. And 30mmol of Fe2+EDTA soaking 500g coke (theoretical load 3.36 ‰)) And then, treating the coke at high temperature under the protection of inert gas to obtain the zero-valent iron with the loading of 1.50 per mill and the utilization rate of the raw material of 45 percent. Therefore, the raw materials of the preparation method provided by the invention have higher utilization rate. The specific surface area of the coke is lower to 0.85m2The specific surface area of the coke loaded with zero-valent iron prepared by soaking and carbothermic method is 3.20m2Per g, the specific surface areas of the composite materials prepared by the fumigation method and containing 0.7 per thousand, 1.1 per thousand, 1.9 per thousand and 2.7 per thousand of iron are 8.61, 9.78, 9.92 and 6.31m2(ii) in terms of/g. The specific surface area of the powdered activated carbon is 857m2The specific surface areas of the activated carbon loaded with zero-valent iron (the amount of the iron source in the raw material is the same) prepared by the liquid phase reduction method, the soaking and carbothermic method and the fumigation method are respectively as follows: 917. 797 and 2212m2(ii) in terms of/g. Therefore, the fumigation method is simple and easy to operate, and the specific surface area of the porous raw material is greatly improved. In addition, the crystal form of the zero-valent iron loaded by the fumigation method is regular compared with that of the liquid phase reduction method.
The porous material loaded with the superfine nano zero-valent iron is used as an adsorbent and a catalyst, and the adsorption, Fe-C micro-electrolysis technology and Fenton oxidation technology are utilized to remove high-toxicity inorganic and organic pollutants in water. Although porous materials such as coke, clay minerals and activated carbon have certain adsorption removal capacity on methyl orange pollutants, the adsorption capacity of the materials on methyl orange is low, and the reusability of the materials is poor. After the nano zero-valent iron is loaded, the reduction capability of the zero-valent iron enhances the redox removal capability of the composite material on methyl orange. After hydrogen peroxide is added, the removal capability of pollutants is greatly improved, and the material can be repeatedly utilized.
Compared with the porous material loaded with the zero-valent iron prepared by the conventional method, the porous material loaded with the superfine nano zero-valent iron prepared by the invention has the following advantages:
(1) the preparation method is simple, easy to operate and free of organic solvent. The conventional impregnation method needs to add organic solvents such as ethanol, polyethylene glycol and the like and organic dispersing agents, so that Fe is convenient2+Entering the inner pore channels of the porous material, and continuously introducing nitrogen to prevent Fe2+Oxidation and precipitation. The method provided by the invention does not need the complicated and time-consuming load of Fe2+And (4) ion process.
(2) The loaded zero-valent iron has small grain diameter and good uniformity. Due to Fe in the high temperature treatment process2+And the chelating action is carried out with organic ligands such as EDTA and the like, thereby being beneficial to generating the monoatomic or zero-valent iron nanocluster. Inside and outside the coke pore canal with larger pore diameter, Fe/C film like spider web can be formed, thereby increasing the surface area and adsorption sites of the porous material.
(3) The prepared porous material loaded with the superfine nano zero-valent iron has higher removal efficiency on organic pollutants such as methyl orange and the like. In the high-temperature treatment process, organic ligands in the raw materials are carbonized and deposited on the surface of the nano zero-valent iron to form a core-shell Fe @ C structure. The newly generated graphitized carbon layer improves the adsorption capacity of the porous material to organic pollutants; the loaded nano iron has small particle size and high surface activity, and is beneficial to the in-situ generation of active ingredients such as hydrogen peroxide, hydroxyl free radicals and the like on the surfaces of particles in an aqueous solution, so that the mineralization of organic pollutants is accelerated.
Methyl orange is selected as a representative of common high-toxicity organic pollutants, and the performance of the porous material loaded with the superfine nano zero-valent iron prepared by the fumigation method is tested. Taking the coke loaded with the nano zero-valent iron as an example, 8g of the coke loaded with the nano zero-valent iron is weighed and added into 80mL of methyl orange solution, the concentration of the methyl orange is 50mg/L, and the pH value of the solution is adjusted to 4.0. Within 3.5h, the adsorption removal rate of the coke not loaded with zero-valent iron on methyl orange is 44.2%, and the removal rate of the coke loaded with zero-valent iron prepared by the dipping method and the carbothermic method on methyl orange is 64%. The removal rate of the zero-valent iron nanocluster-loaded coke prepared by the fumigation method provided by the invention to methyl orange is 70-100%. The removal rate increased with increasing iron loading. Removing methyl orange again from each coke used, and reducing the removal rate of the coke not loaded with zero-valent iron to 22%; the removal rate of the coke loaded with zero-valent iron obtained by the impregnation method and the carbothermic method to methyl orange is 34 percent; the removal rate of the zero-valent iron nanocluster-loaded coke prepared by the fumigation method to methyl orange is 62-100%. When the coke is repeatedly used for the third time, the adsorption removal rate of the coke on the methyl orange is still 22 percent; the removal rate of the coke loaded with zero-valent iron obtained by the impregnation method and the carbothermic method to methyl orange is 25 percent; the removal rate of the zero-valent iron nanocluster-loaded coke prepared by the fumigation method to methyl orange is 60-78%. When the concentration of methyl orange is 200mg/L and the dosage of powdered activated carbon is 0.5g/L, the adsorption removal rate of the methyl orange in 30min is 60 percent; and the activated carbon loaded with zero-valent iron prepared by the fumigation method completely adsorbs and removes methyl orange within 5 s. In a word, compared with the porous material loaded with the zero-valent iron prepared by the conventional method, the porous material loaded with the superfine nano zero-valent iron prepared by the invention has higher removal efficiency on methyl orange pollutants.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic diagram of the synthesis of the porous material loaded with ultra-fine nano zero-valent iron of the present invention;
FIG. 2 is a TEM photograph of the porous material loaded with ultra-fine nano zero-valent iron of the present invention;
FIG. 3 is an SEM photograph of the porous material loaded with ultra-fine nano zero-valent iron of the present invention;
FIG. 4 is an XRD spectrum of the porous material loaded with ultra-fine nano zero-valent iron of the present invention;
FIG. 5 is a BET curve of the porous material loaded with ultra-fine nano zero-valent iron.
Detailed Description
The present invention is further illustrated below with reference to preferred examples, which are only illustrative and not intended to limit the scope of the present invention.
Example 1: the invention discloses a preparation method of a porous material loaded with superfine nano zero-valent iron
The synthesis schematic diagram of the porous material loaded with the superfine nano zero-valent iron is shown in figure 1, and the specific preparation method comprises the following steps:
firstly, weighing a certain proportion of organic iron salt and organic ligand, and mixing with a porous material: for the powdery porous material, the powdery porous material can be directly mixed with organic iron salt and a ligand in a mortar; for the block porous material, the solid powder of organic iron salt and ligand can be adhered on the surface of the block material, or can be scattered in the middle of the material. Adding the obtained mixed solid into a crucible, and heating at the high temperature of 700-1100 ℃ for 1-4 hours under the protection of inert gas to obtain the porous material adsorbent/catalyst loaded with the superfine particle nano zero-valent iron.
Example 2: structural characterization of porous material loaded with superfine nano zero-valent iron
The present embodiment is a structural characterization of a porous material loaded with ultra-fine nano zero-valent iron, specifically as follows:
1.TEM
and analyzing the particle size and the morphology of the porous material loaded with the superfine nano zero-valent iron by adopting a high-resolution transmission electron microscope JEM-2100F, JEOL (Japanese Hitachi).
FIG. 2A shows that superfine zero-valent iron/graphitized carbon composite material can be obtained by high-temperature heating under the protection of organic iron salt and ligand inert gas; FIG. 2B shows the composite material loaded with ultra-fine zero-valent iron prepared by a fumigation method using activated carbon as a carrier. From these figures, it can be seen that the zero valent iron produced by the "fumigation" method has a diameter of about 2-6nm and is uniformly dispersed on the carbon nanosheet layer. When the carrier is activated carbon, the nano zero-valent iron can be uniformly dispersed in the pore canal and the inner and outer surfaces of the activated carbon, and the particle size of the zero-valent iron nano particles is between 2 and 6 nm.
2.SEM
And analyzing the particle size and the morphology structure of the blocky coke material loaded with the superfine nano zero-valent iron by using a field emission scanning electron microscope field + energy spectrometer (FE-SEM + EDAX) (SU-8020+ Model550 i).
FIGS. 3A and 3B are coke loaded with zero-valent nano-iron by the "fumigation method"; fig. 3C shows coke loaded with zero-valent nano-iron by the dipping + carbothermic method. These pictures show that the zero-valent iron loaded onto the coke surface by the "fumigation process" is a spherical structure with a small and uniform particle size. The loading capacity of zero-valent iron in the pore channels of the inner and outer surface areas of the coke is increased along with the increase of the organic iron salt in the raw materials, and when the ratio of the organic iron salt to the coke is 0.9:45, a layer of newly generated composite material of the zero-valent iron and the graphitized carbon is suspended in the pore channels of the coke, so that the adsorption sites of the coke are greatly increased. In the composite material prepared by the traditional impregnation and carbothermic method, the loading capacity of zero-valent iron is small, the zero-valent iron has two shapes of a rod shape and a spherical shape, and the particle size of the zero-valent iron is obviously larger than that of the zero-valent iron prepared by the fumigation method.
XRD spectrum
The X-ray diffraction (XRD) pattern of the ultra-fine nano zero-valent iron-loaded activated carbon was obtained on a b/max-RB diffraction meter (Rigaku, Japan) using nickel filtered Cu Ka rays, with a scanning range from 10 to 80 ℃ and a scanning speed of 4 DEG/min.
As shown in fig. 4, on the XRD spectrogram of the activated carbon loaded with ultra-fine nano zero-valent iron, the diffraction peak at 4.5 ° represents the mesoporous structure of the material; the diffraction peak of 26.4 ° comes from the (002) crystal face of the graphitized carbon; diffraction peaks at diffraction angles of 44.6 and 65.0 ° represent the (110) and (200) crystal planes of α -Fe having a body-centered structure (JCPDS 06-0696), respectively; the surface material contains a certain amount of Fe when the diffraction angles of the diffraction peaks are 30, 35.4, 43.5, 56.8 and 62.4 DEG3O4. While the XRD spectrum of the material prepared by the liquid reduction method can observe diffraction peaks of 4.5 and 26.4 degrees and diffraction peaks of ferric oxide, and no diffraction peak of alpha-Fe is detected. The result shows that the high-temperature heat treatment zero-valent iron has a more regular crystal form.
BET Curve
The specific surface area and the pore size distribution of the activated carbon loaded with the superfine nano zero-valent iron are measured by using a specific surface area and porosity analyzer Micromeritics ASAP 2460.
As shown in fig. 5, activated carbon is a typical mesoporous material and has a high specific surface area. After the zero-valent nano iron is loaded by adopting a liquid phase reduction method, the surface area of the activated carbon is slightly increased; the impregnation and carbothermic method is adopted to load zero-valent iron, so that the surface area of the activated carbon is reduced; the adoption of the fumigation method provided by the invention to load zero-valent iron increases the specific surface area of the activated carbon by 2.6 times.
Example 3: the adsorption/catalysis performance test of the porous material loaded with the superfine nano zero-valent iron
In the embodiment, methyl orange is selected as a representative, and the adsorption/catalysis performance of the porous material loaded with the superfine nano zero-valent iron is tested.
The operation steps of the test are as follows: preparing 80mL of 50mg/L methyl orange standard substance, adjusting the pH value of the solution to 4.0, placing the solution in a 100mL polyethylene plastic vial, adding 8g of coke loaded with superfine nano zero-valent iron, shaking the solution in a shaking table, taking 1.0mL of sample at intervals, centrifuging the sample, taking supernatant, and measuring the concentration of methyl orange by using an ultraviolet-visible spectrophotometer. Preparing 50mL of methyl orange standard for the activated carbon powder material loaded with the superfine zero-valent iron, adding 25mg of the activated carbon powder material loaded with the zero-valent iron, shaking in a shaking table, taking 1mL of sample at each period of time, centrifuging, taking supernatant, and measuring the concentration of the methyl orange by using an ultraviolet-visible spectrophotometer.
The methyl orange determination conditions are as follows:
and (3) centrifuging the water sample, taking supernatant, measuring the absorbance of a group of standard solutions by using a 2cm cuvette at the wavelength of 460nm, drawing a standard curve, simultaneously measuring the absorbance of methyl orange in the sample, and obtaining the content of the methyl orange in the sample by using the standard curve.
The results show that compared with the coke, the ultrafine nano zero-valent iron-loaded coke prepared by the fumigation method can continuously remove methyl orange pollutants. The main reason is that active oxygen free radicals (hydrogen peroxide, hydroxyl free radicals and the like) can be generated on the surface of the loaded superfine zero-valent iron, so that Fenton oxidative degradation of pollutants is promoted. The ultrafine nano zero-valent iron-loaded activated carbon material prepared by the fumigation method has a higher specific surface area, so that the activated carbon material has super strong adsorption and removal capacity on methyl orange, and high-concentration methyl orange pollutants can be adsorbed and removed within 1 min.
Claims (7)
1. A preparation method of porous material adsorbent and catalyst loaded with superfine nano zero-valent iron is characterized by comprising the following steps: (1) weighing a certain proportion of organic ferric salt and organic ligand and mixing with the porous substance; (2) adding the mixed solid obtained in the step (1) into a crucible, and heating at the high temperature of 700-; the organic ligand is selected from EDTA, dopamine and chitosan.
2. The method of claim 1, wherein the organic iron salt of step (1) is selected from the group consisting of ferrous acetate, ferrous citrate, and ferric acetylacetonate.
3. The method according to claim 1, wherein the porous material of step (1) is selected from coke and activated carbon.
4. The method of claim 1, wherein the mass ratio of the organic iron salt to the organic ligand in step (1) is 5:1 to 1: 1.
5. The method according to claim 1, wherein when the porous substance in the step (1) is in a powder form, the mass ratio of the porous substance to the organic iron salt is 8:1-100: 1; when the porous substance is in a block shape, the mass ratio of the porous substance to the organic ferric salt is 37.5:1-150: 1.
6. The method as claimed in claim 1, wherein the high temperature heating temperature in step (2) is 700 ℃ and 1000 ℃, and the reaction time is 1-4 hours.
7. The use of the porous material adsorbent and the catalyst loaded with the superfine nano zero-valent iron obtained by the preparation method of claim 1 in adsorption, degradation and mineralization of high-toxicity pollutants in an environmental water sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911268721.XA CN111097414B (en) | 2019-12-11 | 2019-12-11 | Simple method for loading superfine nano zero-valent iron on porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911268721.XA CN111097414B (en) | 2019-12-11 | 2019-12-11 | Simple method for loading superfine nano zero-valent iron on porous material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111097414A CN111097414A (en) | 2020-05-05 |
| CN111097414B true CN111097414B (en) | 2021-10-15 |
Family
ID=70423210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911268721.XA Active CN111097414B (en) | 2019-12-11 | 2019-12-11 | Simple method for loading superfine nano zero-valent iron on porous material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111097414B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530464A (en) * | 2020-05-13 | 2020-08-14 | 盐城工学院 | Preparation method of three-dimensional graphene zero-valent iron-carrying composite material |
| CN111420662A (en) * | 2020-05-14 | 2020-07-17 | 宜兴国际环保城科技发展有限公司 | Neutral Fenton catalyst, preparation and application |
| CN111530424B (en) * | 2020-06-17 | 2022-07-08 | 福州大学 | Copper-loaded modified carbon material adsorbent for efficiently removing gaseous benzene series and preparation method and application thereof |
| CN111889092B (en) * | 2020-07-30 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method of catalyst for decomposing residual hydrogen peroxide in Fenton effluent, catalyst and application of catalyst |
| CN112079342B (en) * | 2020-08-13 | 2022-03-04 | 哈尔滨工业大学 | Method for preparing magnetic biochar from waste biomass |
| CN112047419B (en) * | 2020-08-20 | 2022-05-03 | 哈尔滨工业大学 | Method for treating organic wastewater by rapidly adsorbing and catalytically oxidizing Congo red |
| CN112604703B (en) * | 2020-10-27 | 2021-11-02 | 中国环境科学研究院 | Graphitized carbon loaded nano zero-valent iron material and preparation method and application thereof |
| CN112607832B (en) * | 2020-11-10 | 2021-09-21 | 中国环境科学研究院 | Nano zero-valent iron-carbon material and preparation method and application thereof |
| CN112960726B (en) * | 2021-03-17 | 2024-04-12 | 安徽工业大学 | Iron-carbon composite material and preparation method and application thereof |
| CN113082214A (en) * | 2021-04-26 | 2021-07-09 | 燕山大学 | Drug carrier, drug delivery system, preparation method and application thereof |
| CN113582284A (en) * | 2021-07-26 | 2021-11-02 | 中国科学院江西稀土研究院 | Preparation method of porous carbon loaded zero-valent iron composite material |
| CN113788528B (en) * | 2021-09-13 | 2023-03-28 | 北京城市排水集团有限责任公司 | Water treatment micro filler and preparation method thereof |
| CN114162896B (en) * | 2021-11-23 | 2023-03-24 | 苏州大学 | Nano zero-valent iron-loaded ceramsite and preparation method thereof |
| CN114146709A (en) * | 2021-12-17 | 2022-03-08 | 南京大学 | Iron/polydopamine/carbon composite catalyst with reduction and oxidation dual performance and preparation method and application thereof |
| CN115385436B (en) * | 2022-08-27 | 2023-12-29 | 西南石油大学 | Method for treating sewage by uniformly loading zero-valent iron catalytic particles of core-shell graphene oxide |
| CN115318293B (en) * | 2022-09-15 | 2023-11-17 | 广州大学 | Method for preparing water treatment catalyst by harmless processing of chicken manure and application of water treatment catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014209850A1 (en) * | 2013-06-26 | 2014-12-31 | Corning Incorporated | Methods and apparatus for synthesis of stabilized zero valent nanoparticles |
| CN108745396A (en) * | 2018-04-18 | 2018-11-06 | 北京林业大学 | A kind of nanometer of confinement Zero-valent Iron@spindle-type porous carbon catalytic oxidation method for treating water |
| CN110252305A (en) * | 2019-03-05 | 2019-09-20 | 中国科学院生态环境研究中心 | Keep the preparation and application of the iron-carbon micro-electrolytic material of the long-acting catalytic activity of Fenton system |
-
2019
- 2019-12-11 CN CN201911268721.XA patent/CN111097414B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014209850A1 (en) * | 2013-06-26 | 2014-12-31 | Corning Incorporated | Methods and apparatus for synthesis of stabilized zero valent nanoparticles |
| CN108745396A (en) * | 2018-04-18 | 2018-11-06 | 北京林业大学 | A kind of nanometer of confinement Zero-valent Iron@spindle-type porous carbon catalytic oxidation method for treating water |
| CN110252305A (en) * | 2019-03-05 | 2019-09-20 | 中国科学院生态环境研究中心 | Keep the preparation and application of the iron-carbon micro-electrolytic material of the long-acting catalytic activity of Fenton system |
Non-Patent Citations (2)
| Title |
|---|
| In situ carbothermal reduction synthesis of Fe nanocrystals embedded into N-doped carbon nanospheres for highly efficient U(VI) adsorption and reduction;Kairuo Zhu et al.;《Chemical Engineering Journal》;20170901;第331卷;第395-405页 * |
| MOFs材料对异味气体吸附及其衍生物气敏特性研究;马翔;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20181015(第10期);第B016-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111097414A (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111097414B (en) | Simple method for loading superfine nano zero-valent iron on porous material | |
| Huang et al. | Enhancement of persulfate activation by Fe-biochar composites: Synergism of Fe and N-doped biochar | |
| Xie et al. | Degradation of tetracycline hydrochloride through efficient peroxymonosulfate activation by B, N co-doped porous carbon materials derived from metal-organic frameworks: Nonradical pathway mechanism | |
| Hua et al. | Defect-and nitrogen-rich porous carbon embedded with Co NPs derived from self-assembled Co-ZIF-8@ anionic polyacrylamide network as PMS activator for highly efficient removal of tetracycline hydrochloride from water | |
| Luo et al. | New insights into the formation and transformation of active species in nZVI/BC activated persulfate in alkaline solutions | |
| Xu et al. | Construction of reduced graphene oxide-supported Ag–Cu 2 O composites with hierarchical structures for enhanced photocatalytic activities and recyclability | |
| Ye et al. | MOFs derived 3D sea urchin-like carbon frameworks loaded on PVDF membranes as PMS activator for highly efficient bisphenol A degradation | |
| Chen et al. | 3D graphene aerogels-supported Ag and Ag@ Ag3PO4 heterostructure for the efficient adsorption-photocatalysis capture of different dye pollutants in water | |
| Zhou et al. | Optimizing nanocarbon shell in zero-valent iron nanoparticles for improved electron utilization in Cr (VI) reduction | |
| Huang et al. | In-situ fabrication from MOFs derived MnxCo3-x@ C modified graphite felt cathode for efficient electro-Fenton degradation of ciprofloxacin | |
| Shi et al. | Fabrication of Au/TiO2 nanowires@ carbon fiber paper ternary composite for visible-light photocatalytic degradation of gaseous styrene | |
| Liu et al. | Highly dispersed copper single-atom catalysts activated peroxymonosulfate for oxytetracycline removal from water: Mechanism and degradation pathway | |
| Yao et al. | Synthesis and characterization of iron-nitrogen-doped biochar catalysts for organic pollutant removal and hexavalent chromium reduction | |
| CN112607832B (en) | Nano zero-valent iron-carbon material and preparation method and application thereof | |
| WO2018166417A1 (en) | Synthesis of a thin insoluble hydroxide shell on the surface of magnetic zero-valent metal nanoparticles for environmental remediation | |
| Huang et al. | Enteromorpha prolifera-derived Fe3C/C composite as advanced catalyst for hydroxyl radical generation and efficient removal for organic dye and antibiotic | |
| Gao et al. | Zeolitic Imidazolate Framework 8‐Derived Au@ ZnO for Efficient and Robust Photocatalytic Degradation of Tetracycline | |
| CN111939960A (en) | Preparation method and application of nitrogen-doped three-dimensional graphene aerogel loaded nano zero-valent iron | |
| Li et al. | MOF derived porous Co@ C hexagonal-shaped prisms with high catalytic performance | |
| Peng et al. | Electropositive carbon sites and sulfur vacancies in SnS2/g-C3N4 for achieving adsorption and photocatalytic degradation of As (III) in stages by pH regulation | |
| Ma et al. | Synthesis of magnetic biomass carbon-based Bi 2 O 3 photocatalyst and mechanism insight by a facile microwave and deposition method | |
| Shenoy et al. | Preparation and characterization of porous iron oxide dendrites for photocatalytic application | |
| Ding et al. | Waste biomass derived carbon supported Mo2C/C composite materials for heavy metal adsorption and hydrogen evolution reaction | |
| Yang et al. | Synergistic activation of peroxymonosulfate by MnO/Fe3C encapsulated in N-doped carbon nanosheets for the enhanced degradation of bisphenol A | |
| Chang et al. | Jointly augmented photocatalytic NO removal by S-scheme Bi12SiO20/Ag2MoO4 heterojunctions with surface oxygen vacancies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |