CN110734133B - Nano zero-valent iron-nickel composite porous material, preparation method and application thereof - Google Patents
Nano zero-valent iron-nickel composite porous material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nano zero-valent iron-nickel composite porous material, a preparation method and application thereof, belonging to the technical field of water treatment, wherein the preparation method of the nano zero-valent iron-nickel composite porous material comprises the following steps: step S1, preparing nanometer zero-valent iron-nickel powder by taking natural laterite-nickel ore as a raw material; step S2, mixing the nano zero-valent iron-nickel powder with zeolite, cement, aluminum powder, quicklime, gypsum and a surfactant, and preparing a crude filler through pouring, foaming, cutting and autoclaving maintenance; and step S3, uniformly spreading the nano zero-valent iron-nickel powder on the surface of the rough filler, performing water dispersion curing, and then performing natural curing to obtain the nano zero-valent iron-nickel composite porous material. The nano zero-valent iron-nickel composite porous material prepared by the invention has a high-openness pore structure, and has higher biological activity, adsorption performance and ion exchange performance when being used as an artificial wetland substrate.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a nano zero-valent iron-nickel composite porous material, a preparation method and application thereof.
Background
With the continuous development of industrialization and economy, the problem of water pollution brings long-term serious harm to the health of human beings and organisms, especially the pollution caused by organic pollutants and heavy metal ions in water. Compared with the traditional sewage treatment technology, the artificial wetland system has the obvious advantages of low investment, low operation cost and the like, has become a sewage treatment technology with higher economic benefit and environmental benefit, is widely applied to treating various domestic sewage and industrial wastewater at home and abroad, mainly utilizes the interaction among the filler matrix, the aquatic plants and the microorganisms in the wetland, and purifies sewage through a series of physical, chemical and biological ways, wherein the filler in the system plays an important role in the wetland sewage treatment process, is a main place for sewage treatment, and removes pollutants through the actions of interception, filtration, adsorption, precipitation and the like.
At present, a filler matrix of the artificial wetland mainly comprises materials such as soil, fine sand, coarse sand, gravel, broken tiles or ash slag, steel slag and the like, but the filler formed by simply stacking the materials generally has the defects of insufficient mechanical strength, easy blockage, low nitrogen and phosphorus adsorption capacity and the like, and the purification efficiency of the artificial wetland on sewage is severely limited by the limited performances such as porosity, specific surface area and the like.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of a nano zero-valent iron-nickel composite porous material, which comprises the following steps:
step S1, preparing nanometer zero-valent iron-nickel powder by taking natural laterite-nickel ore as a raw material;
step S2, mixing the nano zero-valent iron-nickel powder with zeolite, cement, aluminum powder, quicklime, gypsum and a surfactant, and preparing a composite porous material through pouring, foaming, cutting and autoclaving maintenance;
and step S3, uniformly spreading the nano zero-valent iron-nickel powder on the surface of the composite porous material, and naturally curing after water dispersion and curing to obtain the nano zero-valent iron-nickel composite porous material.
Optionally, step S1 specifically includes: crushing and screening the natural laterite-nickel iron ore; and calcining the mixture in a reducing atmosphere to obtain the nano zero-valent iron-nickel powder.
Optionally, the calcination temperature of the calcination under the reducing atmosphere is 200-600 ℃, and the calcination time is 2-5 h.
Optionally, the reducing atmosphere of the calcining under a reducing atmosphere comprises hydrogen.
Optionally, the crushing and screening the natural laterite-nickel iron ore comprises: crushing and screening natural laterite-nickel iron ore to obtain laterite-nickel iron ore powder with the particle size less than or equal to 0.0037 mm.
Optionally, the mass ratio of the nano zero-valent iron-nickel powder to the zeolite, the cement, the aluminum powder, the quicklime, the gypsum and the surfactant is 12:2:2:2:1:1: 1.
Optionally, the foaming condition in step S2 is 3.0h to 3.5h at 60 ℃.
Optionally, in the step S2, the autoclave curing condition is constant pressure autoclave curing for 4 to 12 hours, and the autoclave curing temperature is 180 ℃.
The invention also provides the nano zero-valent iron-nickel composite porous material prepared by the preparation method of the nano zero-valent iron-nickel composite porous material.
The invention also provides application of the nano zero-valent iron-nickel composite porous material in constructed wetlands.
Compared with the prior art, the invention has the beneficial effects that:
the nanometer zero-valent iron-nickel powder prepared from natural laterite-nickel ore has higher chemical activity and catalytic activity, and compared with the existing filler, the nanometer zero-valent iron-nickel composite porous material prepared by taking the nanometer zero-valent iron-nickel powder as a main raw material and utilizing the aerated concrete block production method has higher biological activity, adsorption performance and ion exchange performance;
2, the prepared nano zero-valent iron-nickel composite porous material has a high-openness pore structure, provides a structural foundation for high load of microorganisms, provides a good environment for growth of the microorganisms, and is beneficial to degradation of the microorganisms to pollutants;
3, the nano zero-valent iron-nickel composite porous material has a large specific surface area, and can effectively adsorb, filter and intercept pollutants;
4, the nano zero-valent iron-nickel composite porous material contains nano zero-valent iron-nickel powder, the nano zero-valent iron-nickel powder contains nano zero-valent nickel, and the nano zero-valent nickel is oxidized into Ni2+On the one hand, the chemical reaction rate can be accelerated, and on the other hand, Ni2+Can promote the growth of anaerobic microorganisms, so that the nano zero-valent iron-nickel composite porous material has the functions of oxidizing ammonia nitrogen and denitrifying denitrification.
5, the production process of the nano zero-valent iron-nickel composite porous material is mature, reliable and convenient, the existing aerated concrete production process can be used as production equipment, the degree of mechanization is high, and the production cost is low.
Drawings
FIG. 1 is an XRD pattern of a nano zero-valent iron-nickel composite porous material in an embodiment of the invention;
FIG. 2 is a Micro-CT image of the outer surface of the nano zero-valent iron-nickel composite porous material in the embodiment of the invention;
FIG. 3 is a Micro-CT image of the inner surface of the nano zero-valent iron-nickel composite porous material in the embodiment of the invention;
FIG. 4 is a photomicrograph of protozoa and metazoa in the nano zero-valent iron-nickel composite porous material-constructed wetland system with a resolution of 1 μm according to the embodiment of the invention;
FIG. 5 is a photomicrograph of protozoa and metazoa in the nano zero-valent iron-nickel composite porous material-constructed wetland system at a resolution of 20 μm according to the embodiment of the invention;
FIG. 6 is an SEM image of the outer surface pores of the porous composite material of zero-valent iron and nickel in the constructed wetland system;
fig. 7 is an SEM image of the nano zero-valent iron-nickel composite porous material-constructed wetland system in which microorganisms are loaded on the nano zero-valent iron-nickel composite porous material according to the embodiment of the present invention.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The embodiment of the invention provides a preparation method of a nano zero-valent iron-nickel composite porous material, which comprises the following steps:
step S1, preparing nanometer zero-valent iron-nickel powder by taking natural laterite-nickel ore as a raw material;
step S2, mixing the nano zero-valent iron-nickel powder with zeolite, cement, aluminum powder, quicklime, gypsum and a surfactant, and preparing a composite porous material through pouring, foaming, cutting and autoclaving maintenance;
and step S3, uniformly spreading the nano zero-valent iron-nickel powder on the surface of the composite porous material, and naturally curing after water dispersion curing to obtain the nano zero-valent iron-nickel composite porous material.
According to the invention, firstly, the nano zero-valent iron-nickel powder is prepared by taking laterite-nickel ore as a raw material, and the method comprises the following specific steps: and crushing and screening the laterite-nickel ore to obtain laterite-nickel ore powder with the particle size of less than or equal to 0.0037mm, and calcining the laterite-nickel ore powder in a reducing atmosphere to obtain the nano zero-valent iron-nickel powder. The laterite-nickel iron ore is crushed to increase the unsmooth degree of the surface of the laterite-nickel iron ore and further increase the specific surface area of the laterite-nickel iron ore, the larger the specific surface area of the laterite-nickel iron ore is, the more dangling bonds are on the surface of the laterite-nickel iron ore, the larger the adsorption capacity of reaction molecules is, and the larger the specific surface area of the laterite-nickel iron ore is, the more catalytic active sites are, so that the catalytic capacity is correspondingly enhanced.
Wherein the reducing atmosphere comprises hydrogen, the calcining temperature is 200-600 ℃, and the calcining time is 2-5 h. The laterite-nickel ore mainly comprises hematite, goethite and nickel oxide, when the laterite-nickel ore is calcined in a hydrogen atmosphere, the hematite and goethite are reduced into nanometer zero-valent iron, the nickel oxide is reduced into nanometer zero-valent nickel, and main chemical reaction equations are shown in formulas (1) to (3):
Fe2O3+3H2＝2Fe0+3H2O (1)
2FeOOH+3H2＝2Fe0+4H2O (2)
NiO+H2＝Ni0+H2O (3)
secondly, preparing a composite porous material, mixing the nano zero-valent iron-nickel powder, the zeolite, the cement, the aluminum powder, the quicklime, the gypsum and the surfactant according to the mass ratio of 12:2:2:2:1:1, adding water, stirring and mixing for 30min to prepare mixed slurry.
The zeolite is used as a framework of the composite porous material, the natural clinoptilolite is preferably used as the cement, the cement is used as a binder, the aluminum powder is used as a foaming agent, the content of the aluminum powder is 99%, the calcium lime provides alkalinity, the particle size of the calcium lime is less than 0.0037mm, the content of the calcium lime is more than 90%, the gypsum is used as a coagulant, the content of the gypsum is 90%, and the surfactant comprises washing powder or saponin powder.
Putting the mixed slurry into a mould, putting the mould into a heat preservation box for gas generation to prepare a block, wherein the temperature in the heat preservation box is 60 ℃, the gas generation time is 3.0-3.5 h, taking the mould out of the heat preservation box, taking the block out of the mould, cutting the block into cubes with the size of 10mm by using a brick cutter, putting the cubes into a high-pressure reaction kettle, and autoclaving at 180 ℃ for 4-12 h to prepare the composite porous material, wherein the composite porous material has rich open pore structures,
and S3, after the composite porous material is cooled, uniformly spreading the nano zero-valent iron-nickel powder on the surface of the composite porous material to enable the nano zero-valent iron-nickel powder to fall into the pore channels inside the open pores of the composite porous material, then uniformly spraying water on the surface of the composite porous material, and naturally curing the composite porous material for 5-30 days to obtain the nano zero-valent iron-nickel composite porous material.
The nanometer zero-valent iron-nickel composite porous material is prepared by reducing and calcining natural laterite-nickel ore to obtain the nanometer zero-valent iron-nickel powder, mixing, foaming, high-temperature steam-pressing and forming, and finally uniformly scattering the nanometer zero-valent iron-nickel powder by using natural zeolite powder as a framework, high-strength portland cement as a binder, aluminum powder as a foaming agent, calcium lime for providing alkalinity, gypsum as a coagulant and washing powder or saponin powder as a surfactant. The raw materials used are abundant in resources, low in price, mature and reliable in preparation method, high in mechanization degree and low in production cost, and the existing aerated concrete production process can be used as production equipment.
The invention adopts natural laterite-nickel ore to prepare nano zero-valent iron-nickel powder, the nano zero-valent iron-nickel composite powder contains nano zero-valent iron and nano zero-valent nickel, and the nano zero-valent nickel is oxidized into Ni2+On the one hand, accelerate the nano zero-valent iron Fe0The electron transfer rate of the composite porous material is improved, the chemical reaction rate is further improved, the specific reaction mechanism is shown in the formulas (4) to (12), the nano zero-valent iron-nickel powder Fe/Ni preferentially catalyzes and oxidizes micro pollutants, reaction sites are formed on the surface of the composite porous material, a micro primary battery is promoted to be formed to generate hole charges, the corrosion to the nano zero-valent iron-nickel powder Fe/Ni is accelerated, the catalytic oxidation capability of the nano zero-valent iron-nickel powder Fe/Ni is improved, and the degradation of the micro pollutants is promoted. The introduction of the nano zero-valent Ni metal can effectively improve the catalytic performance of the iron-based material, mainly because fine Ni metal particles are uniformly distributed in the material to serve as catalytic active sites.
Fe0+2H+→Fe2++H2(9)
Fe0+2H2O→Fe2++H2+2OH-(10)
2Ni0+H2→2Ni-H(11)
Ni-H→Ni0+H*(12)
On the other hand Ni2+Can promote the growth of anaerobic microorganisms to attach various microorganisms to the microorganismThe microorganism forms redox zones on the outer surface and the inner part of the nano zero-valent iron-nickel composite porous material, and has the functions of oxidizing ammonia nitrogen and denitrifying denitrification.
XRD (X-ray diffraction) test is carried out on the nano zero-valent iron-nickel composite porous material, and the result is shown in figure 1. Wherein: ca represents calcium oxide; h represents hematite; Fe-Ni represents nano zero-valent iron nickel; according to fig. 1, the nano zero-valent iron-nickel composite porous material contains nano zero-valent iron-nickel, hematite and calcium oxide, which indicates that the nano zero-valent iron-nickel composite porous material has been successfully prepared.
In another embodiment of the invention, the prepared nano zero-valent iron-nickel composite porous material is used in an artificial wetland, the nano zero-valent iron-nickel composite porous material is used as an artificial wetland filler, an artificial wetland system is constructed by the nano zero-valent iron-nickel composite porous material and aquatic plants such as water hyacinth, watermifoil, narcissus, chlorophytum comosum and the like, and wastewater rich in nitrogen and phosphorus is introduced into the artificial wetland system for purification treatment.
The plant (such as aquatic plant or marsh plant), microorganism (bacteria and fungi) and the nano zero-valent iron-nickel composite porous material jointly form an interdependent organic system. The microorganisms in the artificial wetland system are the main force for degrading pollutants in the water body, the aerobic microorganisms decompose most organic matters in the wastewater into carbon dioxide and water through the respiration effect, the anaerobic bacteria decompose organic matters into carbon dioxide and methane, the nitrifying bacteria nitrify ammonium salts, and the denitrifying bacteria reduce nitrate nitrogen into nitrogen. Through the series of actions, main organic pollutants in the sewage can be degraded and assimilated to become a part of microbial cells, and the rest of inorganic substances which are harmless to the environment return to the nature. In addition, some protozoa and metazoan exist in the artificial wetland ecosystem, and insects and birds in the artificial wetland system can also participate in engulfming organic particles deposited in the wetland system, and then carry out assimilation, so that the organic particles are absorbed as nutrient substances, and particulate matters in sewage are removed to some extent.
The nano zero-valent iron-nickel composite porous material prepared by the invention has high open porosity, so that various microorganisms can be attached to the outer surface and the inner part of the nano zero-valent iron-nickel composite porous material, and the microorganisms form redox sub-bands on the outer surface and the inner part of the nano zero-valent iron-nickel composite porous material and have the functions of oxidizing ammonia nitrogen and denitrifying denitrification. The nano zero-valent iron-nickel composite porous material prepared by the invention can be used as an excellent microbial carrier material with biological activity, and provides a place for the propagation and growth of microorganisms. Meanwhile, the nano zero-valent iron-nickel composite porous material used as a filler has the function of synchronous denitrification and dephosphorization in the artificial wetland, and can selectively adsorb ammonia nitrogen in water.
In the artificial wetland system, oxygen is brought into the nano zero-valent iron-nickel composite porous material dispersed around the plant rhizome by the plant rhizome, but the environment far away from the plant root is still in an anaerobic state, so that an environment change region is formed, and the capacity of removing complex pollutants (refractory organic matters) and nitrogen and phosphorus of the artificial wetland can be improved. The removal of most organic pollutants and nitrogen-phosphorus compounds in sewage can depend on microorganisms in the mechanism, but certain pollutants such as heavy metal, sulfur, phosphorus and the like can reduce the concentration thereof through the nano zero-valent iron-nickel composite porous material and plant absorption. On one hand, the nano zero-valent iron-nickel composite porous material can exchange, adsorb and remove ammonia nitrogen ions in wastewater, on the other hand, in the drainage intermission period or drainage valley period of the artificial wetland, the loaded microorganisms can convert ammonia nitrogen into nitrate so as to realize the regeneration of zeolite in the nano zero-valent iron-nickel composite porous material, and further load iron oxidizing bacteria and anaerobic ammonium oxidizing bacteria depending on the nitrate. Ammonia nitrogen adsorbed by the nano zero-valent iron-nickel composite porous material is converted into nitrate by aerobic ammonia oxidizing bacteria, then is washed by the artificial wetland system and enters the sewage, and the nitrate in the artificial wetland system is converted into nitrogen by denitrifying bacteria in the sewage, so that the removal of total nitrogen is facilitated, the Chemical Oxygen Demand (COD) in the sewage is consumed in the denitrification process, and the COD load of the sewage treatment system is reduced. A small amount of organic matters existing in gaps of the nano zero-valent iron-nickel composite porous material are used as a carbon source, nitrate is degraded, and meanwhile, ferrous minerals can be oxidized to generate ferric hydroxide by relying on nitrate type iron oxidizing bacteria. In addition, the anaerobic condition formed by the self structure of the nano zero-valent iron-nickel composite porous material enables the denitrification reaction to be thorough, and further improves the removal effect of nitrate nitrogen.
The nano zero-valent iron-nickel composite porous material has the function of adsorbing ammonia nitrogen in water, is a high-efficiency microbial carrier material, efficiently removes nitrogen and phosphorus in wastewater, and has the function of adsorbing various organic pollutants in water. The nano zero-valent Ni is oxidized into Ni2+Not only can accelerate the electron transfer rate of nano-iron and improve the chemical reaction rate, but also Ni2+Also can promote the growth of anaerobic microorganisms. The nano zero-valent iron-nickel composite porous material can be applied to constructed wetland substrates, is used as a carrier material of microorganisms, has the function of synchronous denitrification and dephosphorization, and is particularly suitable for the treatment of eutrophic wastewater.
Example one
The preparation steps of the nano zero-valent iron-nickel composite porous material are as follows:
1.1 calcining natural laterite-nickel ore serving as a raw material for 3 hours at the temperature of 400 ℃ in a hydrogen atmosphere to obtain nano zero-valent iron-nickel powder;
1.2, weighing the nano zero-valent iron-nickel powder, the natural zeolite powder, the high-strength portland cement, the aluminum powder, the quicklime, the gypsum and the washing powder according to the mass ratio of 12:2:2: 1:1:1, carrying out batching, mixing, casting and foaming on the raw materials, then carrying out autoclaved forming at 180 ℃, wherein the foaming time is 3.5 hours and the autoclaved time is 8 hours, and finally uniformly spraying the nano zero-valent iron-nickel powder, dispersing water and curing for 20 days to obtain the nano zero-valent iron-nickel composite porous material;
and carrying out Micro-computer tomography scanning Micro-CT on the nano zero-valent iron-nickel composite porous material, wherein the result is shown in figures 2-3. The nano zero-valent iron-nickel composite porous material has rough and porous inner and outer surfaces, the pore channel structure of the nano zero-valent iron-nickel composite porous material presents three-dimensional connectivity, the nano zero-valent iron-nickel composite porous material has high porosity and high hydrophilicity, wherein the porosity is 85% -95%, and the high porosity provides space for microorganisms to enter the nano zero-valent iron-nickel composite porous material for adhesion and growth, so that the nano zero-valent iron-nickel composite porous material is very suitable for the growth of the microorganisms.
The average mesoporous diameter of the nano zero-valent iron-nickel composite porous material is 10 nm-50 nm and the specific surface area is 90m measured by a nitrogen adsorption and desorption curve2/g～114m2The specific surface area of the nano zero-valent iron-nickel composite porous material is larger, so that ion exchange adsorption is facilitated, the loading capacity of microorganisms is higher, and the pollutant removal effect is further improved.
In this embodiment, the nano zero-valent iron-nickel composite porous material and a commercially available artificial wetland substrate are respectively filled into two artificial wetland systems under the same conditions for pilot test operation and comparison test, and the removal of nitrogen, phosphorus and pollutants thereof is investigated. Wherein, the ammonia nitrogen concentration of the inlet water of the artificial wetland system is 10 mg/L-300 mg/L, the total nitrogen concentration is 10 mg/L-350 mg/L, the COD concentration is 10 mg/L-200 mg/L, and the P concentration is 0.1 mg/L-5 mg/L.
According to pilot test results, the removal rate of ammonia nitrogen of the nano zero-valent iron-nickel composite porous material-artificial wetland system formed by the nano zero-valent iron-nickel composite porous material reaches more than 97% after the system is operated for about one year, the total nitrogen removal rate reaches more than 86%, the COD removal rate reaches more than 94%, and the P removal rate reaches more than 97%. And the commercial artificial wetland substrate-artificial wetland system consisting of the commercial artificial wetland substrate has the ammonia nitrogen removal rate of 60 percent, the total nitrogen removal rate of 36 percent, the COD removal rate of 64 percent and the P removal rate of 47 percent when the system is operated for about one year.
By analyzing the composition and characteristics of the protozoa and metazoan in the nano zero-valent iron-nickel composite porous material-artificial wetland system, the nano zero-valent iron-nickel composite porous material has a good effect on sewage treatment when being used in the artificial wetland. Fig. 4-5 are photographs under a microscope of protozoa and metazoans in the nano zero-valent iron-nickel composite porous material-artificial wetland system, and it is observed from fig. 4 and 5 that the protozoas and metazoans in the nano zero-valent iron-nickel composite porous material-artificial wetland include rotifers, nematodes, oligocaterpillars, ciliates, tickworms and sipunculus. Because the rotifer is sensitive to organic matters and oxygen deficiency, when dissolved organic matters are decomposed into inorganic matters and nitrogen elements are converted into nitrate, the rotifer can appear only when DO content in the wastewater is normal, so that the appearance of the rotifer also reflects that the effluent quality in the nano zero-valent iron-nickel composite porous material-artificial wetland system can reach the national discharge standard. The sippy-straw insect is sensitive to oxygen deficiency, and the existence of the sippy-straw insect indicates that the oxygen supply of the microorganism in the nano zero-valent iron-nickel composite porous material-artificial wetland system is good. The nematode is sensitive to organic matters but not particularly sensitive to oxygen, and the appearance of the nematode shows that organic matters in the nano zero-valent iron-nickel composite porous material-artificial wetland system are degraded greatly, and the aerobic biological membrane is mature and stable.
The results of SEM tests on the nano zero-valent iron-nickel composite porous material-artificial wetland system are shown in FIGS. 6-7, and the nano zero-valent iron-nickel composite porous material can be observed to have a macroporous structure which is communicated with each other and uniformly distributed, and most of the nano zero-valent iron-nickel composite porous material is distributed in the range of 10-20 μm. Fig. 6 shows the pore structure of the outer surface of the nano zero-valent iron-nickel composite porous material, and the pore opening of the nano zero-valent iron-nickel composite porous material can be observed to be wedge-shaped. The high-porosity and three-dimensional communicated macroporous structure is favorable for exerting the biological conductivity of the nano zero-valent iron-nickel composite porous material, namely favorable for the adhesion growth of microorganisms, the entry of nutrients and oxygen required by the microorganisms and the discharge of metabolites. FIG. 7 is an SEM photograph of the nano zero-valent iron-nickel composite porous material loaded with microorganisms. In the 7 th to 15 th days of operation of the nano zero-valent iron-nickel composite porous material-artificial wetland system, a large number of microorganisms are adhered to the nano zero-valent iron-nickel composite porous material, most of the microorganisms are filamentous and rod-shaped strains, and the distribution of the microorganisms is uneven. According to the phenomenon observed by SEM, the nano zero-valent iron-nickel composite porous material has a rough surface and is suitable for the propagation and growth of microorganisms.
The nano zero-valent iron-nickel composite porous material prepared by the invention is used as an artificial wetland substrate, and has higher pollutant removal rate compared with the artificial wetland substrate sold in the market, mainly because the nano zero-valent iron-nickel composite porous material has rough surface and higher porosityProvides favorable conditions for the propagation and growth of microorganisms, and is an excellent microorganism carrier material; and the nano zero-valent Ni in the nano zero-valent iron-nickel composite porous material can be oxidized into Ni2+，Ni2+Can also promote the growth of anaerobic microorganisms. In addition, the nano zero-valent iron-nickel composite porous material has a large specific surface area, and can effectively adsorb, filter and intercept pollutants.
Example two
2.1 calcining natural laterite-nickel ore serving as a raw material for 5 hours at the temperature of 200 ℃ in a hydrogen atmosphere to obtain nano zero-valent iron-nickel powder;
2.2, weighing the nano zero-valent iron-nickel powder, the natural zeolite powder, the high-strength portland cement, the aluminum powder, the quicklime, the gypsum and the saponin powder according to the mass ratio of 12:2:2: 1:1:1, carrying out batching, mixing, casting and foaming on the raw materials, then carrying out autoclaved forming at a high temperature of 180 ℃, wherein the foaming time is 3 hours and the autoclaved time is 4 hours, and finally uniformly spraying the nano zero-valent iron-nickel powder, dispersing water and curing for 5 days to obtain the nano zero-valent iron-nickel composite porous material;
and 2.3 filling the nano zero-valent iron-nickel composite porous material and a commercial artificial wetland substrate into two artificial wetland systems under the same condition respectively to perform pilot test operation and comparison test, and inspecting the removal of nitrogen, phosphorus and pollutants thereof.
Wherein the ammonia nitrogen concentration of the inlet water of the artificial wetland system is 10 mg/L-200 mg/L, the total nitrogen concentration is 10 mg/L-276 mg/L, COD concentration is 15 mg/L-150 mg/L, and the P concentration is 0.2 mg/L-6 mg/L.
According to pilot test results, the removal rate of ammonia nitrogen of the nano zero-valent iron-nickel composite porous material-artificial wetland system formed by the nano zero-valent iron-nickel composite porous material reaches more than 94% after the system is operated for about one year, the total nitrogen removal rate reaches more than 88%, the COD removal rate reaches more than 96%, and the P removal rate reaches more than 97%. And the commercial artificial wetland substrate-artificial wetland system consisting of the commercial artificial wetland substrate has the ammonia nitrogen removal rate of 50 percent, the total nitrogen removal rate of 34 percent, the COD removal rate of 54 percent and the P removal rate of 57 percent when the system is operated for about one year.
EXAMPLE III
3.1 calcining the natural laterite-nickel ore serving as a raw material for 2 hours at the temperature of 600 ℃ in a hydrogen atmosphere to obtain nano zero-valent iron-nickel powder;
3.2, mixing the components in a mass ratio of 12:2:2:2:1:1, weighing the nano zero-valent iron-nickel powder, natural zeolite powder, high-strength portland cement, aluminum powder, quicklime, gypsum and a surfactant, mixing, casting and foaming the raw materials for 3.5 hours, putting the raw materials into an autoclave curing kettle, performing autoclave curing for 12 hours at the pressure of 12MPa and the temperature of 180 ℃, and finally uniformly scattering the nano zero-valent iron-nickel powder, dispersing water and curing for 30 days to obtain the nano zero-valent iron-nickel composite porous material;
3.3 filling the nano zero-valent iron-nickel composite porous material and a commercial artificial wetland substrate into two artificial wetland systems under the same condition respectively to carry out pilot test operation and comparison test, and investigating the removal of nitrogen, phosphorus and pollutants thereof.
Wherein, the ammonia nitrogen concentration of the inlet water of the artificial wetland system is 10 mg/L-150 mg/L, the total nitrogen concentration is 10 mg/L-100 mg/L, COD concentration is 10 mg/L-150 mg/L, and the P concentration is 0.1 mg/L-2 mg/L.
According to pilot test results, the removal rate of ammonia nitrogen of the constructed wetland system made of the nano zero-valent iron-nickel composite porous material reaches more than 93 percent, the total nitrogen removal rate reaches more than 85 percent, the COD removal rate reaches more than 98 percent, and the P removal rate reaches more than 99 percent when the constructed wetland system is operated for about one year. And the commercial artificial wetland substrate-artificial wetland system consisting of the commercial artificial wetland substrate has the ammonia nitrogen removal rate of 67 percent, the total nitrogen removal rate of 44 percent, the COD removal rate of 64 percent and the P removal rate of 27 percent when the system is operated for about one year.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of a nano zero-valent iron-nickel composite porous material is characterized by comprising the following steps:
step S1, preparing nanometer zero-valent iron-nickel powder by taking natural laterite-nickel ore as a raw material; the method specifically comprises the following steps: crushing and screening the natural laterite-nickel ore to obtain laterite-nickel ore powder with the particle size of less than or equal to 0.0037mm, and calcining the laterite-nickel ore powder in a reducing atmosphere to obtain the nano zero-valent iron-nickel powder;
step S2, mixing the nano zero-valent iron-nickel powder with zeolite, cement, aluminum powder, quicklime, gypsum and a surfactant, and preparing a composite porous material through pouring, foaming, cutting and autoclaving maintenance;
and step S3, uniformly spreading the nano zero-valent iron-nickel powder on the surface of the composite porous material, and naturally curing after water dispersion curing to obtain the nano zero-valent iron-nickel composite porous material.
2. The method for preparing the nano zero-valent iron-nickel composite porous material according to claim 1, wherein the calcination temperature in the reducing atmosphere is 200 ℃ to 600 ℃, and the calcination time is 2h to 5 h.
3. The method of preparing a nano zero-valent iron-nickel composite porous material according to claim 2, wherein the reducing atmosphere calcined under a reducing atmosphere comprises hydrogen.
4. The preparation method of the nano zero-valent iron-nickel composite porous material as claimed in any one of claims 1 to 3, wherein the mass ratio of the nano zero-valent iron-nickel powder to the zeolite, the cement, the aluminum powder, the quicklime, the gypsum and the surfactant is 12:2:2:2:1: 1.
5. The method for preparing a nano zero-valent iron-nickel composite porous material according to claim 4, wherein the foaming condition in the step S2 is that gas is generated at 60 ℃ for 3.0h to 3.5 h.
6. The method for preparing a nano zero-valent iron-nickel composite porous material according to claim 5, wherein the autoclave curing condition in the step S2 is constant pressure autoclave curing for 4 to 12 hours, and the autoclave curing temperature is 180 ℃.
7. The nano zero-valent iron-nickel composite porous material prepared by the preparation method of the nano zero-valent iron-nickel composite porous material as claimed in any one of claims 1 to 6.
8. The application of the nano zero-valent iron-nickel composite porous material of claim 7 in constructed wetlands.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0723795A2 (en) * | 1995-01-26 | 1996-07-31 | Dow Corning S.A. | Particulate foam control agents and their use |
| US6261986B1 (en) * | 1998-04-22 | 2001-07-17 | New Mexico Tech Research Foundation | Production and article of iron/surfactant-modified zeolite pellets to retain and destroy water pollutants |
| JP2006307295A (en) * | 2005-04-28 | 2006-11-09 | National Institute Of Advanced Industrial & Technology | Clay composition for porous metal or porous ceramic, and method for producing porous metal or porous ceramic using it |
| CN1915511A (en) * | 2006-08-17 | 2007-02-21 | 南京工业大学 | Bimetallic catalyst for degrading chlorinated organic pollutants in water and preparation method and application thereof |
| CN102225806A (en) * | 2011-05-24 | 2011-10-26 | 合肥工业大学 | Magnetic biological carrier and preparation method thereof |
| CN102531157A (en) * | 2012-03-02 | 2012-07-04 | 合肥工业大学 | Biological aerated filter packing and preparation method thereof |
| CN103086460A (en) * | 2013-02-04 | 2013-05-08 | 合肥工业大学 | Phosphorus-removing method based on nano-grade iron |
| CN104291797A (en) * | 2014-09-26 | 2015-01-21 | 福州大学 | Bamboo-charcoal-shaped porous ceramsite coated by zero-valent iron as well as preparation method and application of bamboo-charcoal-shaped porous ceramsite |
| CN104628138A (en) * | 2015-01-21 | 2015-05-20 | 北京林业大学 | Artificial wetland filler capable of efficiently removing nitrogen and phosphorous and preparation method thereof |
| CN104828928A (en) * | 2014-02-12 | 2015-08-12 | 同济大学 | Preparation method of filtering material of nitrogen and phosphorus removal bio-filter tank |
| CN104909460A (en) * | 2015-05-18 | 2015-09-16 | 上海交通大学 | Porous nitrogen and phosphorus removal filler for artificial wetland and preparation method of porous nitrogen and phosphorus removal filler |
| CN105036256A (en) * | 2015-08-20 | 2015-11-11 | 江苏大学 | Novel microelectrolysis filler, and preparation method and application thereof |
| CN105330022A (en) * | 2015-11-30 | 2016-02-17 | 云南兆泓环境工程有限公司 | Compound filler applied to simultaneous phosphorus and nitrogen removal of artificial wetland |
| CN105819632A (en) * | 2016-05-24 | 2016-08-03 | 安徽美自然环境科技有限公司 | Method for improving ammonium-nitrogen removal rate in discharged water by using zeolite aerated concrete to construct drainage pipe |
| CN106044919A (en) * | 2016-05-24 | 2016-10-26 | 安徽美自然环境科技有限公司 | Method for increasing ammonium nitrogen in river water |
| CN108746604A (en) * | 2018-06-26 | 2018-11-06 | 厦门理工学院 | A kind of air-stable type nano zero valence iron and its preparation method and application |
| CN110002806A (en) * | 2019-04-23 | 2019-07-12 | 南京大学 | A kind of lightweight sustained release denitrogenation dephosphorizing material and the preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100434676B1 (en) * | 2001-06-30 | 2004-06-07 | 영성산업 주식회사 | Porous mineral media for wastewater treatment and manufacturing process of the same |
| CN100420640C (en) * | 2006-05-25 | 2008-09-24 | 甘肃金桥给水排水设计与工程有限公司 | Lightweight highly effective filtering material for biology and its preparation method |
| FR2969513B1 (en) * | 2010-12-22 | 2013-04-12 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A SPHERICAL MATERIAL HIERARCHISED POROSITY COMPRISING METALLIC PARTICLES PIEGEES IN A MESOSTRUCTURED MATRIX |
| KR101484478B1 (en) * | 2014-02-28 | 2015-01-28 | 청호환경개발주식회사 | A functional carrier and the manufacturing method for water treatment system |
| CA2959125C (en) * | 2014-12-05 | 2019-03-12 | Halliburton Energy Services, Inc. | Treatment fluids comprising calcium aluminate cement and methods of use |
| KR101570130B1 (en) * | 2015-05-12 | 2015-11-18 | 동원중공업 주식회사 | Multiple odor absorbents by using mixing the natural zeolite and method of fabricating the same |
| CN109715585A (en) * | 2016-07-28 | 2019-05-03 | 伊梅斯切公司 | Ceramic manufacturing |
| CN107020066A (en) * | 2017-04-06 | 2017-08-08 | 湖南三友环保科技股份有限公司 | The preparation method and application of load hydrogen ferric oxide nano zeolitic material |
| CN109574233B (en) * | 2018-12-18 | 2021-06-25 | 北京工业大学 | Artificial wetland system added with zeolite loaded nano zero-valent iron |
-
2019
- 2019-11-06 CN CN201911075590.3A patent/CN110734133B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0723795A2 (en) * | 1995-01-26 | 1996-07-31 | Dow Corning S.A. | Particulate foam control agents and their use |
| US6261986B1 (en) * | 1998-04-22 | 2001-07-17 | New Mexico Tech Research Foundation | Production and article of iron/surfactant-modified zeolite pellets to retain and destroy water pollutants |
| JP2006307295A (en) * | 2005-04-28 | 2006-11-09 | National Institute Of Advanced Industrial & Technology | Clay composition for porous metal or porous ceramic, and method for producing porous metal or porous ceramic using it |
| CN1915511A (en) * | 2006-08-17 | 2007-02-21 | 南京工业大学 | Bimetallic catalyst for degrading chlorinated organic pollutants in water and preparation method and application thereof |
| CN102225806A (en) * | 2011-05-24 | 2011-10-26 | 合肥工业大学 | Magnetic biological carrier and preparation method thereof |
| CN102531157A (en) * | 2012-03-02 | 2012-07-04 | 合肥工业大学 | Biological aerated filter packing and preparation method thereof |
| CN103086460A (en) * | 2013-02-04 | 2013-05-08 | 合肥工业大学 | Phosphorus-removing method based on nano-grade iron |
| CN104828928A (en) * | 2014-02-12 | 2015-08-12 | 同济大学 | Preparation method of filtering material of nitrogen and phosphorus removal bio-filter tank |
| CN104291797A (en) * | 2014-09-26 | 2015-01-21 | 福州大学 | Bamboo-charcoal-shaped porous ceramsite coated by zero-valent iron as well as preparation method and application of bamboo-charcoal-shaped porous ceramsite |
| CN104628138A (en) * | 2015-01-21 | 2015-05-20 | 北京林业大学 | Artificial wetland filler capable of efficiently removing nitrogen and phosphorous and preparation method thereof |
| CN104909460A (en) * | 2015-05-18 | 2015-09-16 | 上海交通大学 | Porous nitrogen and phosphorus removal filler for artificial wetland and preparation method of porous nitrogen and phosphorus removal filler |
| CN105036256A (en) * | 2015-08-20 | 2015-11-11 | 江苏大学 | Novel microelectrolysis filler, and preparation method and application thereof |
| CN105330022A (en) * | 2015-11-30 | 2016-02-17 | 云南兆泓环境工程有限公司 | Compound filler applied to simultaneous phosphorus and nitrogen removal of artificial wetland |
| CN105819632A (en) * | 2016-05-24 | 2016-08-03 | 安徽美自然环境科技有限公司 | Method for improving ammonium-nitrogen removal rate in discharged water by using zeolite aerated concrete to construct drainage pipe |
| CN106044919A (en) * | 2016-05-24 | 2016-10-26 | 安徽美自然环境科技有限公司 | Method for increasing ammonium nitrogen in river water |
| CN108746604A (en) * | 2018-06-26 | 2018-11-06 | 厦门理工学院 | A kind of air-stable type nano zero valence iron and its preparation method and application |
| CN110002806A (en) * | 2019-04-23 | 2019-07-12 | 南京大学 | A kind of lightweight sustained release denitrogenation dephosphorizing material and the preparation method and application thereof |
Non-Patent Citations (7)
| Title |
|---|
| Impacts of Binder-Zeolite Interactions on the Structure and Surface Properties of NaY-SiO2 Extrudates;Chen, NY等;《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》;20150902;第54卷(第34期);全文 * |
| Preparation and characterization of ceramic foam supported nanocrystalline zeolite catalysts;Buciuman, FC等;《CATALYSIS TODAY》;20010915;第69卷;全文 * |
| 沸石同步脱氮除磷功能调控及机理研究;贺银海;《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》;20180815(第8期);全文 * |
| 等 沸石加气混凝土生物填料制备及其序批式脱氮水处理;边佳等;《中国环境科学》;20170620;第37卷(第6期);全文 * |
| 致孔剂对多孔羟基磷灰石微球的孔结构的影响;余盛等;《浙江理工大学学报》;20150710;第33卷(第7期);全文 * |
| 超声/沸石载钴活化过硫酸盐降解染料废水研究;尹翠琴等;《佳木斯大学学报(自然科学版)》;20180315;第36卷(第2期);全文 * |
| 陶粒表面涂覆改性及其吸附性能研究;王耀龙;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20120915(第9期);全文 * |
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