CN110734127B - Carbon composite nano zero-valent metal porous functional material, and preparation method and application thereof - Google Patents
Carbon composite nano zero-valent metal porous functional material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon composite nano zero-valent metal porous functional material, a preparation method and application thereof. The preparation method of the carbon composite nano zero-valent metal porous functional material comprises the following steps: the meteorite powder is used as a raw material and is subjected to reduction calcination to prepare the nano zero-valent metal composite material; mixing zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant, and performing pouring, foaming, cutting and autoclaved curing to obtain a composite porous material; and uniformly spreading the nano zero-valent metal composite material on the surface of the composite porous material, and naturally curing after water dispersion curing to obtain the carbon composite nano zero-valent metal porous functional material. The material prepared by the invention has multi-level pores, higher porosity and larger specific surface area, provides space for microorganisms to enter the interior of the carbon composite nano zero-valent metal porous functional material for attachment growth, can be used as an artificial wetland substrate or a sponge city substrate for treating wastewater, and has high pollutant removal rate.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a carbon composite nano zero-valent metal porous functional material, and 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 the advantages of low investment, low operation cost and the like, and is widely applied to the treatment of industrial wastewater. The artificial wetland system mainly utilizes the interaction among the filler matrix, the aquatic plants and the microorganisms in the wetland to purify the 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, 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.
In addition, with the acceleration of the urbanization process, the problems of urban waterlogging, water resource shortage, increased runoff pollution and the like are obvious. According to the information of the national environmental protection agency, the runoff of rainwater has been listed as the 3 rd pollution source causing water pollution. Since the technical guidance for sponge city construction published in 10 months 2014, urban runoff reduction and collection, rainwater purification and reasonable utilization become the key points of urban construction in new period of China and are one of the focuses of water environment research. The key point of sponge city construction is that the natural accumulation, natural penetration and natural purification of rainwater are realized through the combination of artificial facilities and natural ways, and the rainwater can be released in the absence of water, so that good natural circulation is formed, and the utilization of rainwater resources and the ecological environment protection are promoted. The urban rainwater runoff generation has randomness and intermittence, and the pollution source has the characteristics of wide distribution, no concentration, large change of pollutant concentration and the like. How to effectively collect, purify and store the urban runoff rainwater is one of the key problems to be solved. The urban non-hardened underlying surface is fully utilized, and on the basis of keeping the original life and ecological functions, the effective way for solving the problems is to promote the rainwater to permeate, purify and store on site through the combined action of the soil, the plants and the microorganism system. In recent years, research on reduction of surface water pollution and urban rainfall runoff pollution by using a soil infiltration principle has attracted much attention. In the 70 s of the 20 th century, various types of surface runoff storage and runoff pollution reduction in green lands have been utilized abroad, wherein optimization of the filling matrix of the underlay surface in the non-hardening area is an effective way for improving the rainwater treatment performance of the system, at present, research on the urban underlay surface only stays in the aspects of traditional sand matrix proportioning optimization and layered filling, the rainwater permeation speed is limited in space improvement, and the pollutant reduction amount cannot meet the recycling standard easily.
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 one aspect of the above problems, the present invention provides a method for preparing a carbon composite nano zero-valent metal porous functional material, comprising 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 material is obtained by calcining the meteorite powder and the biomass powder in an atmosphere of hydrogen or carbon monoxide.
Optionally, in the step S1, the calcination is performed in an atmosphere of hydrogen or carbon monoxide, 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 a carbon composite nano zero-valent metal porous functional material prepared by the preparation method of the carbon composite nano zero-valent metal porous functional material.
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 specific surface area of the carbon composite nano zero-valent metal porous functional material is 70-250m2/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 the carbon composite nano zero-valent metal porous functional material in artificial wetland.
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 a carbon composite nano zero-valent metal porous functional material, 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 nano zero-valent metal composite material with high activity is obtained by pretreating meteorite and biomass respectively, uniformly mixing the meteorite powder and the biomass powder according to the mass ratio of 1:1-3:1, introducing into reducing atmosphere for calcining, and naturally cooling to room temperature in an oxygen-free atmosphere. Wherein the reducing atmosphere comprises hydrogen or carbon monoxide; the calcining temperature of the reduction calcining is 400-900 ℃, and the calcining 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 one of 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.
Meteorites are small solid fragments derived from the asteroid or comet, originating in outer space, which have an effect on both the earth's surface and on organisms. The meteorites are called meteors before they strike the ground, and range in size from small to very large. When the meteor body enters the earth's atmosphere, it rises in temperature and glows due to friction, pressure and the chemical action of atmospheric gases, thus forming a meteor, including a fireball, also known as a dart. A spark is both an extraterrestrial body that collides with the earth and an abnormally bright spark that, like a fireball, eventually affects the surface of the earth anyway. More generally, any meteor at the earth's surface is a natural object from outer space. Meteorites are also found in the moon and in the mars. Observed passage through the atmosphere or impingement on the earth for merle is called medium merle, and the other merles are called found merle. By 2 months 2010, only about 1086 samples with no meteorites were collected, but 38660 confirmed samples with no meteorites were found. Meteorites are generally divided into three major classes: the meteorite is mainly a rock, the composition of which is mostly silicate minerals; iron meteorite, a large proportion of which is iron and nickel; the composition of merle has both abundant rocks and metals. Modern meteorites are classified according to their structure, chemical isotope and mineralogy, with meteorites less than 2 mm classified as micrometalites. The meteorites in the invention mainly comprise tergites, conoids, merle or ferronickel meteorites.
The meteorite mainly comprises transition metals such as iron, nickel, manganese, arsenic, molybdenum, zirconium, niobium, ruthenium, rhodium, silver, cadmium, indium, cobalt, palladium, tin, antimony and the like. Because of the large amount of transition metal contained in the meteorite, the transition metal oxide has the following properties: the d electron layer of the metal cation in the transition metal oxide volatilizes electrons or takes electrons, and has stronger redox performance; the transition metal oxide has semiconductor properties; the inner valence orbitals and the external orbitals of the metal ions in the transition metal oxide can be split; the transition metal oxide and the transition metal can be used as oxidation-reduction reaction catalysts, and the former has strong heat resistance and toxicity resistance, and has photosensitive, thermosensitive and impurity sensitivity, so that the performance of the catalyst can be adjusted more easily, and the application is wider; the transition metals Fe, Co and the like can form stronger synergistic action with Ni metal, and can also obviously improve the catalytic activity of the Ni-based catalyst.
The invention relates to a nano zero-valent metal composite material prepared by taking meteorite as a raw material, which mainly comprises nano zero-valent iron, nano zero-valent nickel, nano zero-valent copper and nano rare metal. In the prior art, a passivation layer, such as iron hydroxide precipitate, is formed on the surface of zero-valent iron particles in a catalytic reaction, so that the activity of nano-iron is reduced. The nano zero-valent metal composite material prepared by the invention contains metal with high reduction potential (such as palladium, copper and nickel), and is a multi-component composite material. In the catalytic reaction, the surface of the multi-metal particle of the nano zero-valent metal composite material forms a primary battery among various metals due to different potential differences of the various metals, so that the activity of metallic iron in the nano zero-valent metal composite material is increased, more electrons are provided to participate in the catalytic reaction, and the catalytic degradation efficiency is improved. Therefore, on one hand, the multi-component composite material can enhance the activity of the metal of the nano zero-valent metal composite material, on the other hand, the metals in the composition of the nano zero-valent metal composite material can play a synergistic role, and the speed and the selectivity of the metal of the nano zero-valent metal composite material participating in the reduction reaction are improved. Therefore, the nano zero-valent metal composite material prepared in the step S1 can form a multi-metal system, and the rate of catalytic reaction is improved.
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.
During the preparation of the composite porous material, the aluminum powder can generate hydrogen in an alkaline solution, and meanwhile, a porous structured material is generated, while the active component of quicklime provides alkalinity to provide an alkaline environment for the pore-forming of hydrogen generated from the aluminum powder, and the main component of calcium oxide reacts with water to release a large amount of heat to raise the temperature of the blank. In order to prevent the heat generated by the reaction of calcium oxide and water from oxidizing the nano zero-valent metal composite material prepared in the step S1, in the step S3, the nano zero-valent metal composite material is uniformly spread on the surface of the prepared composite porous material after the composite porous material is cooled, and the carbon composite nano zero-valent metal porous functional material is prepared after maintenance. The weight ratio of the nano zero-valent composite material to the composite porous material is 1-5:90-100, so that the nano zero-valent metal composite material falls into the pore channels inside the open pores of the composite porous material, water is uniformly sprayed on the surface of the composite porous material, and the composite porous material is naturally cured for 5-30 days, thus obtaining the carbon composite nano zero-valent metal porous functional material.
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 some embodiments, 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 embodiment takes the carbon composite nanoscale zero-valent metal porous functional material as the artificial wetland substrate for detailed description.
The plant (such as aquatic plant or marsh plant), microorganism (bacteria and fungi) and the carbon composite nanometer zero-valent metal porous functional material form a system which is interdependent. 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 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 an excellent microbial carrier material with bioactivity, and provides a place for the propagation and growth of microbes. Meanwhile, the carbon composite nano zero-valent metal porous functional material used as a filler has the function of synchronous nitrogen and phosphorus removal in the artificial wetland, and can selectively adsorb ammonia nitrogen in water.
In the 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, so that an environment change area is formed, and the capability 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 some pollutants such as heavy metal, sulfur, phosphorus and the like can be reduced through the carbon composite nano zero-valent metal porous functional material and plant absorptionLow in its concentration. The carbon composite nanometer zero-valent metal porous functional material can exchange and adsorb ammonia nitrogen ions in wastewater to remove the ammonia nitrogen ions, and on the other hand, in the drainage intermission period or drainage valley period of the artificial wetland, the loaded microorganisms can convert the ammonia nitrogen into nitrate so as to realize the regeneration of zeolite in the carbon composite nanometer zero-valent metal porous functional material and further load iron oxidizing bacteria and anaerobic ammonium oxidizing bacteria depending on the nitrate. In the artificial wetland system, ammonia nitrogen adsorbed by the carbon composite nano zero-valent metal porous functional material is converted into nitrate by aerobic ammonia oxidizing bacteria, then the nitrate 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 carbon composite nano zero-valent metal porous functional material are used as a carbon source, nitrate is degraded, and meanwhile, ferric hydroxide can be generated by oxidizing ferrous minerals by means of nitrate type iron oxidizing bacteria, and the ferric hydroxide has a good adsorption effect on phosphate and can be used for removing the phosphate. The carbon composite nano zero-valent metal porous functional material absorbs phosphorus and chemically reacts with phosphate radical ions, and the removal mechanism is Al in the matrix3+、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 is carried out under neutral or acidic environmental conditions, and it is considered that phosphate ions are adsorbed to Al mainly by ligand exchange3+、Fe3+A surface. 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 further improves the removal effect of nitrate nitrogen.
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, and efficiently removes nitrogen in wastewaterAnd phosphorus, and also has the function of adsorbing various organic pollutants in water. The nano iron in the nano zero-valent metal composite material can be coupled with anaerobic bacteria (such as ammonia oxidizing bacteria), the component is firstly reduced into nitrite and then further reduced into ammonia nitrogen, and the anaerobic ammonia oxidizing bacteria can perform biological conversion by utilizing two substances generated by the system in sequence to realize biological denitrification. In addition, the component can be coupled with a denitrifying bacteria system, so that the reaction time is shortened, and the denitrification reaction rate is accelerated. The carbon composite nano zero-valent metal porous functional material comprises a composite porous material with a porous structure and a nano zero-valent metal composite material with high activity, 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, so that the catalytic degradation efficiency is improved; in addition, 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 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 one
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:
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:
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 a carbon monoxide atmosphere at the calcining temperature of 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 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 3, and it can be seen from Table 3 that the porosity of the carbon composite nano zero-valent metal porous functional material prepared in the embodiment is 43% -88%, and the specific surface area is 100-2The compressive strength is 76-97N.
Table 3:
example four
In this embodiment, the carbon composite nanoscale zero-valent metal porous functional material prepared in the first embodiment 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 examined. 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 carbon composite nano zero-valent metal porous functional material-artificial wetland system formed by the carbon composite nano zero-valent metal porous functional material has the ammonia nitrogen removal rate of more than 97 percent, the total nitrogen removal rate of more than 86 percent, the COD removal rate of more than 94 percent and the P removal rate of more than 97 percent after running 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 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.
The carbon composite nano zero-valent metal porous functional material prepared by the invention is used as an artificial wetland substrate, and has higher pollutant removal rate compared with the commercial artificial wetland substrate, mainly because the surface of the carbon composite nano zero-valent metal porous functional material is rough and has higher porosity, favorable conditions are provided for the propagation and growth of microorganisms, and the carbon composite nano zero-valent metal porous functional material is an excellent microorganism carrier material; and the carbon composite nano zero-valent metal porous functional material comprises a composite porous material with a porous structureThe nano zero-valent metal composite material with high activity can form a multi-metal system, and can play a synergistic role among metals in a catalytic reaction, so that the 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 embodiment, the carbon composite nano zero-valent metal porous functional material prepared in the first embodiment is used as a substrate for wastewater treatment in a sponge city, a pilot run test is performed, and removal of nitrogen, phosphorus and other pollutants in wastewater by the carbon composite nano zero-valent metal porous functional material is examined by using commercially available wastewater treated in a sponge city as a comparative test. Wherein, the concentration of the ammonia nitrogen in the inlet water is 1-100mg/L, the total nitrogen concentration is 1-150mg/L, the COD concentration is 1-100mg/L, and the P concentration is 0.1-10 mg/L.
According to the pilot test results, the carbon composite nano zero-valent metal porous functional material-sponge urban system formed by the carbon composite nano zero-valent metal porous functional material has the ammonia nitrogen removal rate of 100 percent, the total nitrogen removal rate of 100 percent, the COD removal rate of 100 percent and the P removal rate of 100 percent after running for about one year. And the commercial sponge city matrix-sponge city system composed of the commercial sponge city matrix has the ammonia nitrogen removal rate of 40%, the total nitrogen removal rate of 34%, the COD removal rate of 50% and the P removal rate of 33% after running for about one year.
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 is highDegree less than 5 mg.L-1All the standards meet various standards such as road cleaning and fire-fighting water standards in the urban wastewater recycling urban general service water quality index (GB/T18920-.
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)
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