CN110734127A - carbon composite nano zero-valent metal porous functional material, preparation method and application thereof - Google Patents

carbon composite nano zero-valent metal porous functional material, preparation method and application thereof Download PDF

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CN110734127A
CN110734127A CN201911075660.5A CN201911075660A CN110734127A CN 110734127 A CN110734127 A CN 110734127A CN 201911075660 A CN201911075660 A CN 201911075660A CN 110734127 A CN110734127 A CN 110734127A
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valent metal
nano zero
carbon composite
metal porous
functional material
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CN110734127B (en
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吴克
鲍腾
慈娟
金杰
王磊
卫新来
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Hefei University
Hefei College
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention provides carbon composite nano zero-valent metal porous functional materials, a preparation method and application thereof.A preparation method of the carbon composite nano zero-valent metal porous functional materials comprises the following steps of preparing a nano zero-valent metal composite material by taking meteorite powder as a raw material through reduction and calcination, mixing and proportioning zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant, preparing the composite porous material through pouring, foaming, cutting and autoclaving maintenance, uniformly spreading the nano zero-valent metal composite material on the surface of the composite porous material, and naturally maintaining the composite porous material after water dispersion maintenance to prepare the carbon composite nano zero-valent metal porous functional material.

Description

carbon composite nano zero-valent metal porous functional material, preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to carbon composite nano zero-valent metal porous functional materials, a preparation method and application thereof.
Background
Industrial wastewater such as heavy metal and the like has serious environmental pollution and harm to human beings, and compared with the traditional sewage treatment technology, the artificial wetland system has widely applied to the treatment of industrial wastewater due to the advantages of low investment, low operation cost and the like, and the artificial wetland system mainly utilizes the interaction among the filler matrix, aquatic plants and microorganisms in the wetland to purify sewage through 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 of sewage treatment, and removes pollutants through the actions of interception, filtration, adsorption, precipitation and the like.
At present, the filler matrix of the artificial wetland is mainly formed by simply stacking materials such as soil, fine sand, coarse sand, gravel, broken tiles or ash slag, steel slag and the like, but the filler prepared by the method 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.
The urban runoff is classified as the 3 rd pollution source causing water pollution according to the information of the national environmental protection agency, and since the technical guidance for sponge urban construction was published 10 months in 2014, the urban runoff reduction, collection, rainwater purification and reasonable utilization become the key points of the urban construction in the new period of China, and are also the focus of water environment research . the important meaning of sponge urban construction is that rainwater naturally accumulates, naturally permeates and naturally purifies through the combination of artificial facilities and natural approaches, and rainwater can be released during water shortage, so that good natural circulation is formed, rainwater resource utilization and ecological environment protection are promoted, the generation of urban rainwater runoff has randomness and intermittence, the pollution source has the characteristics of flooding, unconcentration, large change of pollutant concentration and the like, how to effectively collect, purify and store urban rainwater is the key point of solving the problem , the problem is that the urban rainwater non-hardened urban runoff is fully utilized, the original life bedding and ecological function of the urban runoff is maintained, the pollution reduction of rainwater is promoted through the research of the conventional rainwater storage and soil reduction, the effective utilization of the ground pollution of urban runoff is improved through the research of the ground surface of the urban rainwater storage, the soil pollution reduction and the effective soil reduction of the environmental pollution of the urban runoff.
Disclosure of Invention
The invention solves the problems that the existing artificial wetland filler and sponge urban matrix are easy to block, low in adsorption capacity and poor in pollutant removal effect.
In order to solve at least aspects of the above problems, the invention provides a preparation method of carbon composite nano zero-valent metal porous functional materials, which comprises the following steps:
step S1, the meteorite powder and the biomass powder are used as raw materials, and the nano zero-valent metal composite material is prepared by reduction and calcination;
step S2, mixing and proportioning zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant, and preparing the composite porous material through pouring, foaming, cutting and autoclaving maintenance;
and step S3, uniformly spreading the nano zero-valent metal composite material on the surface of the composite porous material, and naturally curing the composite porous material after water dispersion and curing to obtain the carbon composite nano zero-valent metal porous functional material.
Optionally, in step S1, the nano zero-valent metal composite is obtained by calcining the meteorite powder and the biomass powder in hydrogen or carbon oxide atmosphere.
Optionally, in the step S1, the calcination is performed in an atmosphere of hydrogen or carbon oxide, the calcination temperature is 400 to 900 ℃, and the calcination time is 2 to 5 hours.
Optionally, in step S1, the particle size of the merle powder and the biomass powder is less than 0.0374 mm.
Optionally, the mass ratio of the meteorite powder to the biomass powder is 1-3: 1.
Optionally, the steam curing in step S2 is performed under the conditions of 1Mpa-2Mpa for 5 h-8 h, and the steam curing temperature is 180 ℃ ± 5 ℃.
Optionally, in step S2, the mass percentages of the zeolite, the cement, the quicklime, the aluminum powder and the gypsum are 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%, respectively.
Optionally, in the step S3, the nano zero-valent metal composite is uniformly sprinkled on the surface of the composite porous material, and the weight ratio of the nano zero-valent composite to the composite porous material is 1-5: 90-100.
The invention also provides carbon composite nano zero-valent metal porous functional materials prepared by the preparation method of the carbon composite nano zero-valent metal porous functional material of any .
Optionally, the carbon composite nano zero-valent metal porous functional material has multi-level pores, including micropores of 1nm to 2nm, mesopores of 10nm to 50nm and macropores of 50nm to 1000 μm.
Optionally, the porosity of the carbon composite nano zero-valent metal porous functional material is 90% to 99%.
Optionally, the carbon composite nano zero-valent metal porous functional materialHas a specific surface area of 70 to 250m2/g。
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon composite nano zero-valent metal porous functional material prepared by the invention has multi-level pores including micropores, mesopores and macropores, and also has higher porosity and larger specific surface area, thereby providing a space for microorganisms to enter the carbon composite nano zero-valent metal porous functional material for adhesion and growth.
(2) The carbon composite nano zero-valent metal porous functional material prepared by the invention contains a nano zero-valent metal composite material, and the carbon composite nano zero-valent metal porous functional material can form a multi-metal system, so that in a catalytic reaction, the metals can play a synergistic role, and the catalytic degradation efficiency is improved; therefore, compared with the traditional constructed wetland filler, the filler has strong adsorption capacity and good pollutant removal effect.
(3) According to the invention, the biomass is added when the carbon composite nano zero-valent metal porous functional material is prepared, and as the biomass can form a pore structure in the calcining process, the specific surface area and the porosity of the carbon composite nano zero-valent metal porous functional material are increased, and the adsorption performance of the carbon composite nano zero-valent metal porous functional material is further improved.
(4) The carbon composite nano zero-valent metal porous functional material prepared by the invention also comprises a zeolite component, wherein the zeolite has the effects of removing nitrogen, ion exchange and adsorption, and calcium hydroxide which can fix phosphate in wastewater and generate hydroxyapatite on the surface of the carbon composite nano zero-valent metal porous functional material so as to achieve the effects of synchronously recovering phosphorus and removing nitrogen.
(5) The preparation method is simple, realizes the recycling of waste, saves resources, and has simple preparation method and lower production cost.
The invention also provides application of carbon composite nano zero-valent metal porous functional materials in artificial wetlands.
The carbon composite nano zero-valent metal porous functional material prepared by the method is used as an artificial wetland substrate for treating wastewater, has high pollutant removal rate and is simple in treatment process.
Drawings
FIG. 1 is an SEM image of the outer surface of a carbon composite nano zero-valent metal porous functional material in an embodiment of the invention;
FIG. 2 is an SEM image of the inner surface of the carbon composite nano zero-valent metal porous functional material in the embodiment of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The invention provides a preparation method of carbon composite nano zero-valent metal porous functional materials, which comprises the following steps:
step S1, the meteorite powder and the biomass powder are used as raw materials, and the nano zero-valent metal composite material is prepared by reduction and calcination;
step S2, mixing and proportioning zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant, and preparing the composite porous material through pouring, foaming, cutting and autoclaving maintenance;
and step S3, uniformly spreading the nano zero-valent metal composite material on the surface of the composite porous material, and naturally curing the nano zero-valent metal composite material after water dispersion and curing to obtain the carbon composite nano zero-valent metal porous functional material.
The method comprises the steps of pretreating meteorite and biomass to obtain meteorite powder and biomass powder respectively, uniformly mixing the meteorite powder and the biomass powder according to the mass ratio of 1:1-3:1, introducing the mixture into reducing atmosphere for calcination, and naturally cooling the mixture to room temperature in an oxygen-free atmosphere to obtain the nano zero-valent metal composite material with high activity, wherein the reducing atmosphere comprises hydrogen or carbon oxide, the calcination temperature of the reduction calcination is 400-one-material 900 ℃, and the calcination time is 2-5 h.
According to the invention, the nano zero-valent metal composite carbon material is generated by adding biomass into meteorite powder and calcining, and the specific surface area and porosity are increased because the biomass can form a pore structure in the calcining process, so that the adsorption performance of the nano zero-valent metal composite carbon material is improved.
The biomass powder is prepared by grinding and sieving any materials in leaves, corncobs, rice hulls, tobacco shreds, sawdust, straws, lotus leaves, walnut shells, waste peach shells or waste paper pulp fibers of a paper mill to obtain the biomass powder with the particle size of less than 0.0374 mm.
The meteorite pretreatment process is specifically as follows: the meteorite is crushed to the grain size of less than 0.0374mm at normal temperature, the meteorite has larger specific surface area under the crushed grain size, the dangling bond on the surface of the meteorite is correspondingly increased, the adsorption quantity of reaction molecules is increased, the catalytic active sites are increased, and the catalytic capability is correspondingly improved. Then the meteorite with the grain diameter less than 0.0374mm is fully mixed and dispersed with alcohol and then dried to obtain the meteorite powder. The meteorite is pretreated, so that the dispersing performance of each active component of the meteorite can be improved, and the catalytic activity is improved.
The meteorites are small solid fragments derived from the asteroid or comet, originating in the outer space, having an effect on both the earth's surface and the organism, called meteorites before they impact the earth's surface, ranging in size from small to very large, when meteorites enter the earth's atmosphere, they rise in temperature and glow due to friction, pressure, and the chemical action of gases in the atmosphere, thus forming meteorites, including the fireball, also called the jet.
The meteorite mainly comprises transition metals such as iron, nickel, manganese, arsenic, molybdenum, zirconium, niobium, ruthenium, rhodium, silver, cadmium, indium, cobalt, palladium, tin and antimony, because the meteorite contains a large amount of transition metals, the transition metal oxide has the following properties that a d electron layer of metal cations in the transition metal oxide volatilizes electrons or abstracts electrons and has stronger redox performance, the transition metal oxide has semiconductor properties, inner valence orbits and external orbits of the metal ions in the transition metal oxide can be split, the transition metal oxide and the transition metals can be used as redox reaction catalysts, the former has strong heat resistance and toxicity resistance and photosensitive, thermosensitive and impurity sensitivity and is more favorable for the performance regulation of the catalysts, so that the application is more universal, and the transition metals such as Fe and Co can form stronger synergistic action with Ni metal and also can obviously improve the catalytic activity of the Ni-based catalysts.
The nanometer zero-valent metal composite material prepared by taking meteorite as a raw material has main phases comprising nanometer zero-valent iron, nanometer zero-valent nickel, nanometer zero-valent copper and nanometer rare metals, in the prior art, a passivation layer is formed on the surface of a zero-valent iron particle in a catalytic reaction, such as iron hydroxide precipitation and the like, so that the activity of the nanometer iron is reduced, the nanometer zero-valent metal composite material prepared by the invention contains metals with high reduction potential (such as palladium, copper and nickel) and is multi-component composite materials, in the catalytic reaction, the surface of the multi-metal particle of the nanometer zero-valent metal composite material has different potential differences of the multiple metals, so that an original battery is formed among the multiple metals, the activity of the metal iron in the nanometer zero-valent metal composite material is increased, more electronic references are provided to the catalytic reaction, the catalytic degradation efficiency is improved, therefore, the multi-component composite material in aspect can enhance the activity of the metals of the nanometer zero-valent metal composite material, in addition, in aspect, the nanometer zero-valent metal composite material can play a synergistic effect, the improvement of the nanometer zero-valent metal composite material composition speed and the selective catalytic reaction of the nanometer zero-valent metal composite material S1, so that the nanometer zero-valent metal composite material can be formed in the step of the invention.
The composite porous material is prepared by using natural zeolite powder as a framework of a porous functional material, using high-strength portland cement as a binder, using aluminum powder as a foaming agent, providing alkalinity to quicklime, using a gypsum coagulant, and washing powder or saponin powder as a surfactant, wherein the mass percentages of the zeolite, the cement, the quicklime, the aluminum powder and the gypsum are respectively 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%, and through material mixing, casting, foaming, block cutting and autoclaved molding. Wherein the zeolite is natural clinoptilolite, the cement is preferably portland cement, the content of aluminum powder is 90-99%, the particle size of quicklime is less than 0.037mm, the content of quicklime is 90-99%, and the content of gypsum is 90-99%. Mixing the raw materials in proportion, adding water, stirring and mixing to obtain mixed slurry, filling the mixed slurry into a mold, and placing the mold in a heat preservation box for gas generation to obtain a block body, wherein the temperature in the heat preservation box is as follows: 60 +/-2 ℃, and the gas generation time is as follows: and 3.0-3.5h, taking the mold out of the heat insulation box, taking the block out of the mold, cutting the block into cubes with the size of 10 +/-5 mm by using a brick cutter, and autoclaving the cubes in a high-pressure reaction kettle at the temperature of 180 +/-5 ℃ for 5-8h to obtain the composite porous material with a rich open pore structure.
In the preparation process of the composite porous material, aluminum powder can generate hydrogen in an alkaline solution, a porous structured material is generated, an active component calcium lime provides alkalinity to provide an alkaline environment for the aluminum powder hydrogen-producing pore-forming, and in addition, , calcium oxide serving as a main component reacts with water to release a large amount of heat to raise the temperature of a blank, in order to prevent the heat generated by the reaction of the calcium oxide with the water from oxidizing the nano zero-valent metal composite material prepared in the step S1, in the step S3 of the invention, the nano zero-valent metal composite material is uniformly coated on the surface of the prepared composite porous material after being cooled, and the carbon composite nano zero-valent metal porous functional material is prepared after maintenance, wherein the weight ratio of the nano zero-valent metal composite material to the composite porous material is 1-5:90-100, so that the nano zero-valent metal composite material falls into pore channels inside open pores of the composite porous material, then water is uniformly sprayed on the surface of the composite porous material, and the carbon composite porous material is naturally maintained for 5-30 days, thus the carbon composite zero-valent metal porous functional material is obtained.
The carbon composite nanometer zero-valent metal porous functional material prepared by the invention has multi-level pores, including micropores of 1nm-2nm, mesopores of 10nm-50nm and macropores of 50nm-1000 mu m. Simultaneously has higher porosity and larger specific surface area, wherein the porosity is 90-99 percent, and the specific surface area is 70-250m2And/g, providing space for microorganisms to enter the carbon composite nano zero-valent metal porous functional material for attachment and growth.
The nano zero-valent metal porous functional material prepared by the invention not only has the property of a nano zero-valent metal composite material, but also comprises a zeolite component, wherein the zeolite has the functions of nitrogen removal, ion exchange and adsorption, and also comprises calcium hydroxide, so that phosphate in wastewater can be fixed, hydroxyapatite is generated on the surface of the carbon composite nano zero-valent metal porous functional material, and the functions of synchronously recovering phosphorus and removing nitrogen are achieved. In addition, the preparation process is simple, the waste recycling is realized, and the production cost is low. Compared with the traditional filler, the invention has strong adsorption capacity and good pollutant removal effect.
In examples, the prepared carbon composite nanoscale zero-valent metal porous functional material is used as an artificial wetland substrate or a sponge city substrate for water treatment, and the examples of the examples are described in detail with the carbon composite nanoscale zero-valent metal porous functional material as the artificial wetland substrate.
The plant (such as aquatic plant or marsh plant, etc.), microorganism (bacteria, fungi, etc.) and the carbon composite nanometer zero-valent metal porous functional material together form a interdependent system, wherein, the microorganism in the artificial wetland system is the main force for degrading pollutants in the water body, the aerobic microorganism decomposes most organic matters in the wastewater into carbon dioxide and water through the respiration, the anaerobic bacteria decomposes organic matters into carbon dioxide and methane, the nitrifying bacteria nitrify ammonium salts, and the denitrifying bacteria reduce nitrate nitrogen into nitrogen gas, through the series of actions, main organic pollutants in the wastewater can be degraded and assimilated to become parts of microorganism cells, and the rest become inorganic wetland harmless substances to the environment and return to the nature.
The carbon composite nano zero-valent metal porous functional 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 carbon composite nano zero-valent metal porous functional material, and the microorganisms form redox bands on the outer surface and the inner part of the carbon composite nano zero-valent metal porous functional material and have the functions of oxidizing ammonia nitrogen and denitrifying denitrification.
The carbon composite nano zero-valent metal porous functional material prepared by the invention can be used as excellent microbial carrier materials with biological activity, provides places for microbial propagation and growth, has the functions of synchronous denitrification and dephosphorization in the artificial wetland as a filler, and can selectively adsorb ammonia nitrogen in water.
In an artificial wetland system, oxygen is brought into the carbon composite nano zero-valent metal porous functional material dispersed around the plant root by the plant root, but the environment far away from the plant root is still in an anaerobic state, thus forming environment change areas, and further improving the capacity of the artificial wetland in removing complex pollutants (refractory organic matters) and nitrogen and phosphorus, most of organic pollutants and nitrogen and phosphorus compounds in sewage can be removed by microorganisms in a mechanism, but certain pollutants such as heavy metal, sulfur, phosphorus and the like can reduce the concentration of the pollutants by the carbon composite nano zero-valent metal porous functional material and plant absorption, and the carbon composite nano zero-valent metal porous functional material can reduce the ammonia nitrogen ions in the wastewaterIn the other aspect, in the drainage intermission period or drainage valley period of the constructed wetland, the loaded microorganisms can convert ammonia nitrogen into nitrate so as to realize the regeneration of zeolite in the carbon composite nano zero-valent metal porous functional material and further load iron oxidizing bacteria and anaerobic ammonium oxidizing bacteria depending on the nitrate, in the constructed wetland system, ammonia nitrogen adsorbed by the carbon composite nano zero-valent metal porous functional material is converted into nitrate by aerobic ammonium oxidizing bacteria and then washed into sewage by the constructed wetland system, and the nitrate in the constructed wetland system is converted into nitrogen by denitrifying bacteria in the sewage, so that the removal of total nitrogen is facilitated, Chemical Oxygen Demand (COD) in the sewage is consumed in the denitrification process, the COD load of the sewage treatment system is reduced, a small amount of organic matters existing in gaps of the carbon composite nano zero-valent metal porous functional material are used as a carbon source, the nitrate is degraded, meanwhile, the nitrate-type iron oxidizing bacteria depending on the nitrate can oxidize ferrous minerals to generate ferric iron hydroxide, the ferric iron hydroxide has good adsorption effect on phosphate, and can be used for removing the phosphate3+、Ca2+、Fe3+The plasma can be reacted with PO4 3-The PO is precipitated and removed by adsorption reaction4 3-In which PO is4 3-With Ca2+Acting under alkaline conditions with Al3+、Fe3+The reaction takes place under neutral or acidic environmental conditions, and it is considered that phosphate ions are adsorbed to Al mainly by ligand exchange3+、Fe3+In addition, the anaerobic condition formed by the self structure of the carbon composite nano zero-valent metal porous functional material enables the denitrification reaction to be thorough, and the removal effect of nitrate nitrogen is further improved .
The carbon composite nano zero-valent metal porous functional material has the function of adsorbing ammonia nitrogen in water, is an efficient microbial carrier material, efficiently removes nitrogen and phosphorus in wastewater, and has the function of adsorbing various organic pollutants in water. Wherein in the nano zero-valent metal composite materialThe carbon composite nano zero-valent metal porous functional material comprises a porous structure composite porous material and a high-activity nano zero-valent metal composite material, the nano zero-valent metal composite material can form a multi-metal system, and in a catalytic reaction, all metals can play a synergistic role to improve the catalytic degradation efficiency, and in addition, the nano zero-valent Ni is oxidized into Ni to be the 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 carbon composite nano zero-valent metal porous functional material can be applied to artificial 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
The preparation method of the carbon composite nano zero-valent metal porous functional material in the embodiment comprises the following steps:
respectively crushing and sieving meteorites and straws to be less than 0.0374mm, mixing the meteorite powder and the leaf powder according to the mass ratio of 3:1 to obtain mixed powder, calcining the mixed powder in a hydrogen atmosphere at the calcining temperature of 600 ℃ for 3 hours to obtain the nano zero-valent metal composite material;
meanwhile, the natural zeolite powder, the high-strength portland cement, the quicklime, the aluminum powder and the gypsum are respectively mixed, cast and foamed according to the mass percentages of 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%, and are autoclaved at the high temperature of 180 ℃ for 6 hours to prepare the composite porous material;
and finally, uniformly scattering the nano zero-valent metal composite material on the surface of the composite porous material, wherein the weight ratio of the nano zero-valent metal composite material to the composite porous material is 5:90, and watering and curing for 10 days to obtain the carbon composite nano zero-valent metal porous functional material.
The performance test of the carbon composite nano zero-valent metal porous functional material prepared in the embodiment is carried out, the results are shown in table 1, and it can be seen from table 1 that the porosity of the carbon composite nano zero-valent metal porous functional material prepared in the embodiment is 64% -98%, and the specific surface area is 123-2The compressive strength is 79-94N.
Table 1:
Figure BDA0002262353580000121
SEM tests were performed on the inner and outer surfaces of the carbon composite nano zero-valent metal porous functional material prepared in this example, and the results are shown in fig. 1-2. As can be seen, the carbon composite nano zero-valent metal porous functional material has rough inner and outer surfaces, rich pore structures and high hydrophilicity, and is very suitable for the propagation and growth of microorganisms.
The average mesoporous diameter of the carbon composite nano zero-valent metal porous functional material is 10-50nm, and the specific surface area is 120-200m measured by a nitrogen adsorption and desorption curve2The carbon composite nano zero-valent metal porous functional material has larger specific surface area, is beneficial to ion exchange adsorption, enables the load of microorganisms to be higher, and further improves the pollutant removal effect.
Example two
The preparation method of the carbon composite nano zero-valent metal porous functional material in the embodiment comprises the following steps:
respectively crushing and sieving meteorite and sawdust to be less than 0.0374mm, mixing the meteorite powder and the leaf powder according to the mass ratio of 2:1 to obtain mixed powder, calcining the mixed powder in a hydrogen atmosphere at the temperature of 900 ℃ for 2 hours to obtain the nano zero-valent metal composite material;
meanwhile, mixing, casting and foaming natural zeolite powder, high-strength portland cement, quicklime, aluminum powder, gypsum and a surfactant according to the mass percentage of 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%, and steaming and pressing at the high temperature of 180 ℃ for 8 hours to prepare the composite porous material;
and finally, uniformly scattering the nano zero-valent metal composite material on the surface of the composite porous material, wherein the weight ratio of the nano zero-valent metal composite material to the composite porous material is 3:100, and watering and curing for 15 days to obtain the carbon composite nano zero-valent metal porous functional material.
The carbon composite nano zero-valent metal porous functional material prepared in the embodiment is subjected to performance test, and the result is shown in table 2, and as can be seen from table 2, the porosity of the carbon composite nano zero-valent metal porous functional material prepared in the embodiment is 58% -85%, and the specific surface area is 70-188m2The compressive strength is 66-87N.
Table 2:
Figure BDA0002262353580000131
EXAMPLE III
The preparation method of the carbon composite nano zero-valent metal porous functional material in the embodiment comprises the following steps:
respectively crushing and sieving meteorites and leaves to be below 0.0374mm, mixing the meteorite powder and the leaf powder according to the mass ratio of 1:1 to obtain mixed powder, calcining the mixed powder in carbon oxide atmosphere at 400 ℃ for 5 hours to obtain the nano zero-valent metal composite material;
meanwhile, mixing, casting and foaming natural zeolite powder, high-strength portland cement, quicklime, aluminum powder, gypsum and a surfactant according to the mass percentage of 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%, and steaming and pressing for 4 hours at the high temperature of 180 ℃ to prepare the composite porous material;
and finally, uniformly scattering the nano zero-valent metal composite material on the surface of the composite porous material, wherein the weight ratio of the nano zero-valent metal composite material to the composite porous material is 1:95, and watering and curing for 5 days to obtain the carbon composite nano zero-valent metal porous functional material.
The carbon composite nano zero-valent metal porous functional material prepared in the embodiment is subjected to performance test, the result is shown in table 3, and as can be seen from table 3, the carbon composite nano zero-valent metal porous functional material prepared in the embodimentThe porosity of the carbon composite nano zero-valent metal porous functional material is 43-88 percent, and the specific surface area is 100-248m2The compressive strength is 76-97N.
Table 3:
example four
In this example, the carbon composite nano zero-valent metal porous functional material prepared in example and a commercially available artificial wetland substrate were respectively filled into two artificial wetland systems under the same conditions for pilot plant operation and comparative experiments to examine the removal of nitrogen, phosphorus and pollutants thereof, wherein the ammonia nitrogen concentration of the inlet water of the artificial wetland system is 10-300mg/L, the total nitrogen concentration is 10-350mg/L, the COD concentration is 10-200mg/L, and the P concentration is 0.1-5 mg/L.
According to the pilot test results, the removal rate of ammonia nitrogen in about years, the total nitrogen removal rate is over 86%, the COD removal rate is over 94%, and the P removal rate is over 97% in the constructed wetland system of the carbon composite nano zero-valent metal porous functional material, whereas the removal rate of ammonia nitrogen in about years, the total nitrogen removal rate is 36%, the COD removal rate is over 64%, and the P removal rate is 47% in the constructed wetland system of the commercial constructed wetland substrate, which is composed of the commercial constructed wetland substrate.
The carbon composite nano zero-valent metal porous functional material prepared by the invention is used as an artificial wetland substrate, has higher pollutant removal rate compared with the commercial artificial wetland substrate, is excellent microorganism carrier materials mainly due to the rough surface and larger porosity of the carbon composite nano zero-valent metal porous functional material, provides favorable conditions for the propagation and growth of microorganisms, and can form a multi-metal system in a catalytic reaction, and the metals can perform a synergistic action in the catalytic reactionThe catalytic degradation efficiency is improved; and the nano zero-valent Ni in the carbon composite nano zero-valent metal porous functional material can be oxidized into Ni2+，Ni2+Can also promote the growth of anaerobic microorganisms. In addition, the carbon composite nano zero-valent metal porous functional material has large specific surface area, and can effectively adsorb, filter and intercept pollutants.
EXAMPLE five
In this example, the carbon composite nano zero-valent metal porous functional material prepared in example was used as a substrate for wastewater treatment in sponge cities to perform a pilot run test, and the removal of nitrogen, phosphorus and other pollutants in wastewater by the carbon composite nano zero-valent metal porous functional material was examined by using commercially available substrate for wastewater treatment in sponge cities as a comparative test, wherein the concentration of ammonia nitrogen in the influent water was 1-100mg/L, the total nitrogen concentration was 1-150mg/L, the COD concentration was 1-100mg/L, and the P concentration was 0.1-10 mg/L.
According to the pilot test results, the removal rate of ammonia nitrogen in about years, the total nitrogen removal rate of 100%, the COD removal rate of 100% and the P removal rate of 100% are achieved in a sponge city system which is a carbon composite nano zero-valent metal porous functional material, and the removal rate of ammonia nitrogen in about years, the removal rate of ammonia nitrogen in about 40%, the removal rate of total nitrogen in about 34%, the removal rate of COD in about 50% and the removal rate of P in about 33% are achieved in a sponge city substrate which is commercially available and is made of sponge city substrates.
The test results are as follows: the carbon composite nano zero-valent metal porous functional material-sponge city system formed by the carbon composite nano zero-valent metal porous functional material has the best effect, the water holding capacity is 50-60%, and the average penetration speed is 5 mm.d-1Theoretically, the rainwater infiltration in the area which is 1 to 45 times of the self area can be borne to the maximum in heavy rainstorm weather, and the concentration of ammonia nitrogen in the effluent is less than 0.1 mg.L-1Total nitrogen concentration is less than 0.5 mg.L-1Total phosphorus concentration less than 0.05 mg.L-1COD concentration is less than 5 mg.L-1All meet the standards of road cleaning, fire-fighting water standard and the like in the index of urban Water quality for Recycling urban general Water (GB/T18920- grade A standard in pollutant discharge standard of a town sewage treatment plant (GB 18918-.
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 (13)

  1. The preparation method of the 1, carbon composite nano zero-valent metal porous functional material is characterized by comprising the following steps:
    step S1, the meteorite powder and the biomass powder are used as raw materials to prepare the nano zero-valent metal composite material through reduction and calcination;
    step S2, mixing and proportioning zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant, and preparing the composite porous material through pouring, foaming, cutting and autoclaving maintenance;
    and step S3, uniformly spreading the nano zero-valent metal composite material on the surface of the composite porous material, and naturally curing the composite porous material after water dispersion and curing to obtain the carbon composite nano zero-valent metal porous functional material.
  2. 2. The method of claim 1, wherein the nano zero valent metal composite material is obtained by calcining the meteorite powder and the biomass powder in hydrogen or carbon oxide atmosphere in step S1.
  3. 3. The preparation method of the carbon composite nano zero-valent metal porous functional material according to claim 2, characterized in that the calcination is carried out in hydrogen or carbon oxide atmosphere, the calcination temperature is 400-900 ℃, and the calcination time is 2-5 h.
  4. 4. The method for preparing the carbon composite nano zero-valent metal porous functional material according to claim 1, wherein the particle sizes of the merle powder and the biomass powder in the step S1 are both less than 0.0374 mm.
  5. 5. The method for preparing the carbon composite nano zero-valent metal porous functional material according to claim 1, wherein the mass ratio of the meteorite powder to the biomass powder is 1:1-3: 1.
  6. 6. The method for preparing the carbon composite nano zero-valent metal porous functional material according to claim 1, wherein the steam curing in the step S2 is performed under the conditions of 1MPa-2MPa for 5-8h at 180 ℃ +/-5 ℃.
  7. 7. The method for preparing the carbon composite nano zero-valent metal porous functional material according to claim 1, wherein the mass percentages of the zeolite, the cement, the quicklime, the aluminum powder and the gypsum in the step S2 are respectively 50-65%, 20-40%, 3-11%, 0.5-2% and 1-5%.
  8. 8. The method for preparing a carbon composite nano zero-valent metal porous functional material according to claim 1, wherein in the step S3, the nano zero-valent metal composite is uniformly sprinkled on the surface of the composite porous material, and the weight ratio of the nano zero-valent composite to the composite porous material is 1-5: 90-100.
  9. 9, carbon composite nano zero-valent metal porous functional materials prepared by the method for preparing the carbon composite nano zero-valent metal porous functional materials as claimed in any of claims 1-8.
  10. 10. The carbon composite nano zero-valent metal porous functional material according to claim 9, wherein the carbon composite nano zero-valent metal porous functional material has multi-level pores including micropores of 1nm to 2nm, mesopores of 10nm to 50nm, and macropores of 50nm to 1000 μm.
  11. 11. The carbon composite nano zero-valent metal porous functional material according to claim 9, wherein the porosity of the carbon composite nano zero-valent metal porous functional material is 90-99%.
  12. 12. The carbon composite nano zero-valent metal porous functional material according to claim 9, wherein the specific surface area of the carbon composite nano zero-valent metal porous functional material is 70-250m2/g。
  13. 13, applications of the carbon composite nanometer zero-valent metal porous functional material as claimed in claim 9 in artificial wetland.
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