CN110734128B - Nano zero-valent metal light porous spherical functional material prepared based on meteorite, and preparation method and application thereof - Google Patents
Nano zero-valent metal light porous spherical functional material prepared based on meteorite, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano zero-valent metal light porous spherical functional material prepared based on meteorite, and a preparation method and application thereof. The preparation method of the light porous spherical functional nano zero-valent metal material comprises the following steps: step S1, the meteorite powder is used as the raw material to prepare the nanometer zero-valent metal composite material through reduction and calcination; step S2, mixing zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant to obtain a mixture; and step S3, uniformly adhering the mixture to the framework by taking the polyethylene porous spherical plastic particles as the framework to prepare the zeolite-based light porous spherical functional material. And step S4, uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to obtain the nano zero-valent metal light porous spherical functional material. The invention has multi-level holes, higher porosity and larger specific surface area, regular shape and light weight.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nano zero-valent metal light porous spherical functional material prepared based on meteorites, and a preparation method and application thereof.
Background
Phosphorus is one of essential nutrients for human life, is mainly stored in the earth crust and exists in the form of phosphorite, and is a non-metal mineral resource difficult to regenerate. Phosphorus flows in a straight line on earth "land → ocean". More than 80% of phosphorus extracted from phosphate rock is used for producing phosphate fertilizer, more than 50% of phosphorus in the phosphate fertilizer which is not absorbed by crops can form surface runoff due to rain wash, and phosphorus which is not absorbed by people and animals in food enters surface water along with excrement under the condition of no sewage treatment; finally, the phosphorus enters the sea along with the natural law of 'the strip river is communicated with the sea'. In addition to the excretion of feces by seabirds on land and the fishing of marine products by humans at sea, phosphorus flowing into the sea is difficult to return to land again during the geological evolution period that humans can witness. Therefore, phosphorus, coal, petroleum and the like are non-renewable valuable natural resources.
The phosphorite is extremely unevenly distributed on the earth and has very limited reserves. Although the basic reserve of the earth phosphate ore is 680 multiplied by 108t (in P)2O5Meter), but the economic reserves are only 1/3, about 220 x 108t. With the increase of population and the increasing of living standard of human beings, the demand of the society for phosphorus is higher and higher. Data display of State statistics office, i 2015The yield of the national phosphate fertilizer reaches 970 multiplied by 104t·a-1(P2O5) And increase amount per year is 50X 104t·a-1. With the growth speed, the usage amount of phosphate fertilizer in China will exceed 2000 multiplied by 10 by 2030 years4t·a-1And the unlimited export of the phosphate rock, the future phosphorus resource consumption of China is extremely remarkable. The statistics in 2015 indicate that the basic reserve of phosphorite in China is 31 multiplied by 108t(P2O5) a. Although 2.7 multiplied by 10 times of oversized high-quality (only can be directly used for producing high-concentration phosphorus compound fertilizer without mineral dressing) phosphorite is discovered in the open air of Guizhou in 7 months in 20178t(P2O5) a, the total reserve of high-grade phosphorite in China is very low, P2O5The reserve of the phosphorus-rich ore resource with the content of more than 30 percent is only 16.6 multiplied by 108t(P2O5) Only half of the base reserves. If the phosphorite is mined according to the current mining mode of 'mining rich and abandoning poor', the phosphorite reserves in China are completely mined, and the 'phosphorus crisis' phenomenon follows.
Therefore, the phosphorus recovery strategy is urgently needed to be considered and implemented in China. Throughout the whole path of phosphorus loss and discharge, the optimal nodes for effectively intercepting/recovering phosphorus are mainly concentrated at the source and tail end of phosphorus discharge; terminal phosphorus recovery refers to the recovery of phosphorus from a wastewater treatment process, statistically about 1.3 Mt.a.annually around the world-1The phosphorus is treated by a sewage treatment plant (counted by P), and the interception, separation and recovery of phosphorus can be realized while sewage treatment is carried out by a modern sewage treatment technology taking a centralized mode as a main stream.
The biological aerated filter fully uses the design ideas of a sewage treatment contact oxidation method and a fast water supply filter for reference, and integrates the characteristics of aeration, high filtration speed, suspended matter interception, regular back washing and the like. The process principle is that a certain amount of granular filter materials with smaller grain diameter are filled in a filter tank, a biological membrane grows on the surface of the filter materials, aeration is carried out in the filter tank, and when sewage flows through the filter tank, the sewage is quickly purified by utilizing the strong oxidation degradation capability of the high-concentration biological membrane on the filter materials, which is a biological oxidation degradation process; meanwhile, when sewage flows through, a large amount of suspended matters in the sewage are intercepted by utilizing the characteristic of small particle size of the filter material and the biological flocculation effect of the biological membrane, and the dropped biological membrane is ensured not to be carried out with water, so that the interception effect is achieved; after a certain time of operation, the filter chamber needs to be backwashed due to the increase of head loss so as to release the trapped suspended matters and renew the biomembrane, which is the backwashing process. The filler is used as a core component of the biological aerated filter, the properties of porosity, biological loading capacity and the like influence the performance of the biological aerated filter, and the research and development of the filler are widely concerned in the biological aerated filter process.
In the current application research of the biological aerated filter filler, most of the research focuses on removing phosphorus, but does not relate to recovering phosphorus, so that a filler which can simultaneously remove nitrogen and recover phosphorus in the biological aerated filter reaction is needed.
Disclosure of Invention
The invention solves the problems that the existing biological aerated filter filler has low porosity and low biological load, and can not realize synchronous denitrification and phosphorus recovery.
In order to solve at least one aspect of the above problems, the present invention provides a method for preparing a light porous spherical functional nano-zerovalent metal material based on meteorites, comprising the following steps:
step S1, the meteorite powder is used as the raw material to prepare the nanometer zero-valent metal composite material through reduction and calcination;
step S2, mixing the zeolite, the cement, the quicklime, the aluminum powder, the gypsum and the surfactant to obtain a mixture;
and step S3, uniformly adhering the mixture to the framework by taking the polyethylene porous spherical plastic particles as the framework to prepare the zeolite light porous spherical functional material.
And step S4, uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to obtain the nano zero-valent metal light porous spherical functional material.
Optionally, in step S1, the nano zero-valent metal composite is obtained by calcining the meteorite powder in an atmosphere of hydrogen or carbon monoxide.
Optionally, the calcination temperature in the hydrogen or carbon monoxide atmosphere in the step S1 is 400 to 900 ℃, and the calcination time is 2 to 5 hours.
Optionally, the size of the merle powder in step S1 is less than 0.0374 mm.
Optionally, the mixture in step S3 is adhered to the pore structure of the porous spherical plastic granules of polyethylene under the mechanical action of the mechanical roller.
Optionally, step S3 specifically includes the following steps:
step S31, putting the porous spherical polyethylene plastic particles into a mechanical roller, and uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material;
step S32, uniformly spraying water into the porous functional material to enable the porous functional material to become spherical particle material under the action of the roller;
and step S33, naturally curing the granular material to obtain the light porous spherical functional material of the nano zero-valent metal.
Optionally, in step S2, the mass ratio of the zeolite, the cement, the quicklime, the aluminum powder, and the gypsum is 50% to 60%: 10% -30%: 1% -15%: 0.1% -2%: 1 to 13 percent.
The invention also provides a nano zero-valent metal light porous spherical functional material prepared by the method for preparing the nano zero-valent metal light porous spherical functional material based on the merle.
Optionally, the light porous spherical functional material of the nanometer zero-valent metal has multi-level pores, including micropores of 1nm to 5nm, mesopores of 10nm to 50nm and macropores of 50nm to 100 nm.
Optionally, the porosity of the light porous spherical functional material of the nano zero-valent metal is 90-99%.
Optionally, the specific surface area of the light porous spherical functional nano zero-valent metal material is 110-250m2/g。
Compared with the prior art, the invention has the following beneficial effects:
(1) the light porous spherical functional material of the nano zero-valent metal prepared by the invention has multi-level pores, higher porosity and larger specific surface area, is beneficial to ion exchange adsorption, and provides space for microorganisms to enter the inside of the composite porous functional material of the nano zero-valent metal for adhesion and growth.
(2) The nanometer zero-valent metal light porous spherical functional material prepared by the invention can accelerate the growth rate of nitrifying bacteria and denitrifying bacteria in the biological filter by adding the nanometer zero-valent metal composite material, and improve the denitrification efficiency of the biological aerated filter.
(3) The nanometer zero-valent metal light porous spherical functional material has a regular shape, is spherical as a whole, and has the advantages of small water flow resistance, difficult blockage and uniform gas and water distribution when being used as a filter material of a biological aerated filter.
(4) The light porous spherical functional material of the nanometer zero-valent metal has light weight and low density, is beneficial to the back washing of the biological aerated filter and reduces the energy consumption of the back washing.
(5) The prepared nanometer zero-valent metal light porous spherical functional material contains a nanometer zero-valent metal composite material, and the nanometer zero-valent metal light porous spherical functional material can form a multi-metal system, so that in the catalytic reaction of biological enzyme, the metals can play a synergistic role, and the catalytic degradation efficiency of the biological enzyme is improved; therefore, the light porous spherical functional material of the nano zero-valent metal has the function of adsorbing ammonia nitrogen in water, is a high-efficiency microbial carrier material, efficiently removes nitrogen in wastewater, and has the function of adsorbing various organic pollutants in water.
(6) The nanometer zero-valent metal light porous spherical functional material prepared by the invention contains calcium oxide, can fix phosphate in water, forms hydroxyapatite precipitate on the surface of the nanometer zero-valent metal light porous spherical functional material, and can fix and recover the phosphate in the water. When the nano zero-valent metal light porous spherical functional material is saturated in adsorption, the nano zero-valent metal light porous spherical functional material is rich in nitrogen and phosphorus, and can be used as a fertilizer for soilless culture of vegetables and fruits, so that the conventional fertilizer is replaced, the recycling of wastes is realized, and a new solution is provided for solving the problem of advanced wastewater treatment in the biological aerated filter.
(7) The raw materials used by the invention have rich resources and low price, the waste recycling is realized, the preparation process is simple, and the production cost is low.
The invention also provides application of the light porous spherical functional nano zero-valent metal material in a biological aerated filter.
The nano zero-valent metal light porous spherical functional material prepared by the invention is used as the filler of the biological aerated filter for treating wastewater, is not easy to block, has high pollutant removal efficiency, and has simple treatment process and low energy consumption.
Drawings
FIG. 1 is a polarized light microscope photograph of a nanometer zero-valent metal lightweight porous spherical functional material in an embodiment of the invention;
FIG. 2 is an infrared spectrum before and after the use of the light porous spherical functional nano zero-valent metal material in a biological aerated filter 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 method for preparing a nano zero-valent metal light porous spherical functional material based on meteorites, which comprises the following steps:
step S1, the meteorite powder is used as the raw material to prepare the nanometer zero-valent metal composite material through reduction and calcination;
step S2, mixing zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant to obtain a mixture;
step S3, taking the porous spherical polyethylene plastic particles as a framework, and uniformly adhering the mixture to the framework to prepare the zeolite-based light porous spherical functional material;
and step S4, uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to obtain the nano zero-valent metal light porous spherical functional material.
The meteorite powder is obtained by pretreating meteorite, and the meteorite powder is used as a raw material and is calcined in reducing atmosphere to obtain the nano zero-valent metal composite material with high activity. Wherein the reducing atmosphere is hydrogen or carbon monoxide; the calcining temperature of the reduction calcining is 400-900 ℃, and the calcining time is 2-5 h.
Further, the merle pretreatment procedure is specifically as follows: and (2) crushing the meteorites to the particle size of less than 0.0374mm at normal temperature, fully mixing and dispersing the meteorites with the particle size of less than 0.0374mm with alcohol, and drying to obtain 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 metals (such as palladium, copper and nickel) with high reduction potential, is a multi-component composite material, and in the catalytic reaction, the surface of the multi-metal particles of the nano zero-valent metal composite material forms a galvanic cell among multiple metals due to different potential differences of the multiple 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.
Further, the zeolite, cement, aluminum powder, quicklime and gypsum are mixed according to a certain mass percentage to prepare a mixture, wherein the weight percentage of the ordinary portland cement is as follows: 10-30%, zeolite 50-60%, quicklime: 1-15%, gypsum: 1-13%, aluminum powder: 0.1 to 2 percent.
The zeolite is natural zeolite powder, portland cement is preferably selected as the cement, the purity of the aluminum powder is 99-100%, the particle size of the quicklime is less than 0.0037mm, the content of the quicklime is 90-100%, the content of the gypsum is 90-100%, and the surfactant comprises washing powder or saponin powder. Thus, through the operation, the components are uniformly mixed, and the nano zero-valent metal composite material is favorably loaded on the porous structure.
Further, the invention takes the polyethylene porous spherical plastic particles as a framework, and the mixture is uniformly adhered on the framework to prepare the zeolite-based light porous spherical functional material. The method comprises the following specific steps:
step S31, putting the porous spherical polyethylene plastic particles into a mechanical roller, and uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material; the mixture can fall into the internal pore structure and the external pore structure of the open pores of the porous spherical polyethylene particles, and the porous spherical polyethylene plastic particles rub against each other under the action of a mechanical roller, so that the mixture is adhered to the surfaces and the internal pores of the porous spherical polyethylene particles.
And step S32, uniformly spraying water into the porous functional material to enable the porous functional material to be spherical under the action of a roller to obtain a spherical particle material, and naturally curing the spherical particle material to obtain the zeolite-based lightweight porous spherical functional material, wherein the natural curing time is 5-30 days.
Further, the invention sprays the nanometer zero-valent metal composite material on the zeolite-based light porous spherical functional material uniformly to obtain the nanometer zero-valent metal light porous spherical functional material.
The invention takes meteorite as a raw material, obtains a nano zero-valent metal composite material with a multi-metal system by reducing and calcining meteorite powder, adds cement as a binder, aluminum powder as a foaming agent, calcium oxide for providing alkalinity, gypsum as a coagulant and washing powder or saponin powder as a surfactant into natural mineral powder zeolite, prepares a mixture by mixing ingredients, and then adheres the mixture to the polyethylene porous spherical plastic particles by taking the polyethylene porous spherical plastic particles as a framework to prepare the zeolite-based light porous spherical functional material. And then uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to obtain the nano zero-valent metal light porous spherical functional material.
The raw materials used by the invention have rich resources and low price, the waste recycling is realized, the preparation process is simple, and the production cost is low.
The light porous spherical functional material of the nanometer zero-valent metal has multi-level pores, including micropores of 1nm to 5nm, mesopores of 10nm to 50nm and macropores of 50nm to 100 nm; meanwhile, the material also has higher porosity, provides space for the microorganism to enter the inside of the nanometer zero-valent metal light porous spherical functional material for adhesion growth, wherein the porosity is 90-99 percent, is favorable for ion exchange adsorption, and the specific surface area is 110-250 m-2/g。
In addition, the light porous spherical functional material of the nano zero-valent metal also has a regular shape, is spherical as a whole, and has the advantages of small water flow resistance, difficult blockage and uniform gas and water distribution when being used as a filter material of the biological aerated filter; and the light porous spherical functional material of the nanometer zero-valent metal has the characteristic of light weight, so that the filter material is easy to suspend when the biological aerated filter system performs backwashing, and the backwashing energy consumption is reduced.
The nanometer zero-valent metal light porous spherical functional material prepared by the invention not only has the property effect of a nanometer zero-valent metal composite material, but also comprises a zeolite component, wherein the zeolite has the nitrogen removal effect and the ion exchange and adsorption effect, and also comprises calcium hydroxide which can fix phosphate in wastewater and generate hydroxyapatite on the surface of the nanometer zero-valent metal light porous spherical functional material, so that the purposes of synchronously recovering phosphorus and removing nitrogen are achieved.
The light porous spherical functional material of the nanometer zero-valent metal has the function of adsorbing ammonia nitrogen in water, is an efficient microbial carrier material, efficiently and synchronously recovers phosphorus and removes nitrogen, and has the function of adsorbing various organic pollutants in water. The nano iron in the nano zero-valent metal light porous spherical functional 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 nanometer zero-valent metal light porous spherical functional material comprises a composite porous material with a porous structure and a nanometer zero-valent metal composite material with high activity, and can form a multi-metal system, and in a catalytic reaction, each metal 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 nanometer zero-valent metal light porous spherical functional material prepared by the invention can accelerate the growth rate of nitrifying bacteria and denitrifying bacteria in the biological filter by adding the nanometer zero-valent metal composite material, and improve the denitrification efficiency of the biological aerated filter.
The nanometer zero-valent metal light porous spherical functional material prepared by the invention can form hydrated silicate in water, can fix phosphate in water, forms hydroxyapatite precipitate on the surface of the nanometer zero-valent metal light porous spherical functional material, and recovers the phosphate in the water. When the nano zero-valent metal light porous spherical functional material is saturated in adsorption, the nano zero-valent metal light porous spherical functional material is rich in nitrogen and phosphorus, and can be used as a fertilizer for soilless culture of vegetables and fruits, so that the conventional fertilizer is replaced, the recycling of wastes is realized, and a new solution is provided for solving the problem of advanced wastewater treatment in the biological aerated filter.
Compared with the traditional biological aerated filter packing, the light porous spherical nano zero-valent metal functional material has higher biological activity, adsorption performance and ion exchange performance, provides a structural foundation for high load of microorganisms due to higher porosity, provides a good environment for growth of the microorganisms, has high microbial load, is beneficial to degradation of the microorganisms on pollutants, and ensures thorough denitrification reaction due to anaerobic conditions formed by the structure of the material so as to further improve the removal effect of nitrate nitrogen.
In some embodiments, the prepared nanometer zero-valent metal light porous spherical functional material is used in a biological aerated filter. Because the light porous spherical functional material of the nanometer zero-valent metal has high open porosity, various microorganisms can be attached to the outer surface and the inner part of the light porous spherical functional material of the nanometer zero-valent metal, and the microorganisms form redox bands on the outer surface and the inner part of the light porous spherical functional material of the nanometer zero-valent metal and have the functions of oxidizing ammonia nitrogen and denitrifying denitrification. The nanometer zero-valent metal light porous spherical 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.
Example one
The preparation method of the light porous spherical functional nano-zero-valent metal material in the embodiment comprises the following steps:
1.1 crushing meteorite to be less than 0.0374mm, mixing with alcohol, dispersing, drying, reducing and calcining the dried meteorite powder in a hydrogen atmosphere at the calcining temperature of 600 ℃ for 3h to prepare the nano zero-valent metal composite material;
1.2 mixing ordinary portland cement, natural zeolite powder, quicklime, gypsum and aluminum powder according to the mass ratio: 10-30% of ordinary portland cement, 50-60% of zeolite, 1-15% of quicklime, 1-13% of gypsum and 0.1-2% of aluminum powder are mixed to prepare a mixture;
1.3, placing the porous spherical polyethylene plastic particles into a mechanical roller, and uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material; wherein the biological porosity of the polyethylene porous spherical plastic particles is 80-90%, the particle size of the spheres is 1-3mm, and the polyethylene porous spherical plastic particles are purchased from Hongxiang plastic industry Co., Ltd in Linyi Lanling county, Shandong province.
Uniformly spraying some water into the porous functional material to enable the porous functional material to be spherical under the action of a roller, and naturally curing the spherical porous functional material for 20 days to obtain the zeolite-based lightweight porous spherical functional material
1.4 uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to prepare the nano zero-valent metal light porous spherical functional material.
The performance test of the light porous spherical functional nano-zero-valent metal material prepared in the present example is shown in table 1, and it can be seen from table 1 that the light porous spherical functional nano-zero-valent metal material has a high porosity and a large specific surface area, wherein the porosity is 93% -94%, and the specific surface area is 130-2/g。
Table 1:
example two
The preparation method of the light porous spherical functional nano-zero-valent metal material in the embodiment comprises the following steps:
2.1 crushing meteorite to be less than 0.0374mm, mixing with alcohol, dispersing, drying, calcining the dried meteorite powder in a hydrogen atmosphere at 900 ℃ for 2h, and preparing the nano zero-valent metal composite material;
2.2 mixing the ordinary Portland cement, the natural zeolite powder, the quicklime, the gypsum and the aluminum powder according to the mass ratio: 10-30% of ordinary portland cement, 50-60% of zeolite, 1-15% of quicklime, 1-13% of gypsum and 0.1-2% of aluminum powder are mixed to prepare a mixture;
2.3 putting the porous spherical polyethylene plastic particles into a mechanical roller, uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material, uniformly spraying water into the porous functional material to enable the porous functional material to be spherical under the action of the roller, and naturally curing the spherical porous functional material for 30 days to obtain the zeolite-based lightweight porous spherical functional material;
2.4 uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to prepare the nano zero-valent metal light porous spherical functional material.
The performance test of the light porous spherical functional nano-zero-valent metal material prepared in the present example is shown in table 2, and it can be seen from table 2 that the light porous spherical functional nano-zero-valent metal material has a high porosity and a large specific surface area, wherein the porosity is 95% -97%, and the specific surface area is 140-2/g。
Table 2:
EXAMPLE III
The preparation method of the light porous spherical functional nano-zero-valent metal material in the embodiment comprises the following steps:
3.1 crushing meteorite to be less than 0.0374mm, mixing with alcohol, dispersing, drying, calcining the dried meteorite powder in a hydrogen atmosphere at the temperature of 400 ℃ for 5 hours, and preparing the nano zero-valent metal composite material;
3.2 mixing the ordinary Portland cement, the natural zeolite powder, the quicklime, the gypsum and the aluminum powder according to the mass ratio: 10-30% of ordinary portland cement, 50-60% of zeolite, 1-15% of quicklime, 1-13% of gypsum and 0.1-2% of aluminum powder are mixed to prepare a mixture;
3.3 putting the porous spherical polyethylene plastic particles into a mechanical roller, uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material, uniformly spraying water into the porous functional material to enable the porous functional material to be spherical under the action of the roller, and naturally curing the spherical porous functional material for 5 days to obtain the zeolite-based lightweight porous spherical functional material;
and 3.4, uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to prepare the nano zero-valent metal light porous spherical functional material.
The performance test of the light porous spherical functional nano-zero-valent metal material prepared in the present example is shown in table 3, and it can be seen from table 3 that the light porous spherical functional nano-zero-valent metal material has a high porosity and a large specific surface area, wherein the porosity is 96% -98%, and the specific surface area is 155-2/g。
Table 3:
example four
The preparation method of the light porous spherical functional nano-zero-valent metal material in the embodiment comprises the following steps:
4.1 crushing meteorite to be less than 0.0374mm, mixing with alcohol, dispersing, drying, calcining the dried meteorite powder in a hydrogen atmosphere at 400 ℃ for 5 hours to prepare the nano zero-valent metal composite material;
4.2 mixing the ordinary Portland cement, the natural zeolite powder, the quicklime, the gypsum and the aluminum powder according to the mass ratio: 10-30% of ordinary portland cement, 50-60% of zeolite, 1-15% of quicklime, 1-13% of gypsum and 0.1-2% of aluminum powder are mixed to prepare a mixture;
4.3 putting the porous spherical polyethylene plastic particles into a mechanical roller, uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material, uniformly spraying water into the porous functional material to enable the porous functional material to be spherical under the action of the roller, and naturally curing the spherical porous functional material for 10 days to obtain the zeolite-based lightweight porous spherical functional material;
4.4 uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to prepare the nano zero-valent metal light porous spherical functional material.
The performance test of the light porous spherical functional nano-zero-valent metal material prepared in the embodiment is shown in Table 4, and the results are shown in Table 4, which shows that the light porous spherical functional nano-zero-valent metal material has high porosity and large specific surface area, wherein the porosity is 93-99%, and the specific surface area is 177-2/g。
Table 4:
EXAMPLE five
This example tests the nano zero-valent metal lightweight porous spherical functional material prepared in example four.
The pore structure of the light porous spherical functional nano-zero-valent metal material is analyzed, and the samples are respectively observed by a polarizing microscope, and the result is shown in figure 1. Wherein, fig. 1 is a photo under a single polarized light of a sample, it can be seen that a black part is a skeleton structure of the nano zero-valent metal lightweight porous spherical functional material, mainly comprising natural minerals, nano zero-valent iron and nickel and cement hydration products, and a gray part is pores in the nano zero-valent metal lightweight porous spherical functional material. The average pore diameter of open pores in the light porous spherical functional nano zero-valent metal material prepared by the method is 10-100 mu m through a polarizing microscope, the size of a microorganism individual is 0.1, the size of the microorganism individual means that the microorganism can be propagated and grown in the open pores, and the pore structure of the light porous spherical functional nano zero-valent metal material provides a structural basis for high load of the microorganism.
The specific surface area of the nano zero-valent metal light porous spherical functional material is 110-250m measured by a nitrogen adsorption and desorption curve2The specific surface area of the nanometer zero-valent metal light porous spherical functional material is larger, which is beneficial to ion exchange adsorption, so that the load capacity of microorganisms is higher, and the pollutant removal effect is further improved.
The infrared spectrogram of the nanometer zero-valent metal light porous spherical functional material before and after the use of the biological aerated filter is shown in figure 2, wherein a curve A in the figure 2 represents the infrared spectrogram of the nanometer zero-valent metal light porous spherical functional material before the use, a curve B represents the infrared spectrogram of the nanometer zero-valent metal light porous spherical functional material after the use of the biological aerated filter, a ordinate Transmitance in the figure 2 represents a Transmittance, and an abscissa Wave represents a wavelength. The wavelength detection range of infrared spectrum is 400cm-1-4000cm-1Wherein 414cm-1And 883cm-1Vibration peaks at are respectively SiO4And AlO4And Al-O and Si-O bending vibration. In 549cm-1The Fe-O-Fe bond of the iron oxide is formed. At 594cm-1Si-O-Ca bonds are observed. At 1442cm-1Is treated with CO3 -，1641cm-1The adsorption zone and the gap are combined with water. After the nano zero-valent metal light porous spherical functional material is used in the biological aerated filter, the infrared spectrum of the nano zero-valent metal light porous spherical functional material is 1019cm-1A new peak appears, which corresponds to OH-Stretching vibration and is considered to be a characteristic band of hydroxyapatite. The nanometer zero-valent metal light porous spherical functional material is generated on the surface of the hydroxyapatite after being used, thereby realizing the recovery of phosphorus and the removal of nitrogen in the biological aerated filter.
EXAMPLE six
In the embodiment, the nanometer zero-valent metal lightweight porous spherical functional material prepared in the fourth embodiment is used as a filler to be applied to a biological aerated filter for sewage treatment, and a commercially available filler is used for comparison.
Inoculating sludge used in the test is taken from activated sludge in an oxidation ditch of a municipal sewage treatment plant, firstly, the nano zero-valent metal light porous spherical functional material and the commercially available filler are respectively put into a barrel filled with the activated sludge to be soaked for 3 days, and the weight ratio of the nano zero-valent metal light porous spherical functional material to the commercially available filler is C: n: p is 100: 5: 1 adding nutrient substances.
Then the soaked light porous spherical nano zero-valent metal functional material and the soaked commercially available filler are respectively added into a reactor to form a biological aerated filter system and a biological aerated filter system, microorganisms are inoculated by closed aeration, the aeration amount is controlled by a flowmeter to be 2L/h-5L/h, the system is changed into small flow inlet water after 2 days, the gas-water ratio is kept between 1-10: L, yellow or tawny biological films appear at the bottom of the reactor when the system continuously operates for about 7 days, and microorganisms such as blue algae, paramecium, coccid, a large amount of filamentous bacteria and the like are observed and found by a microscope.
In the experiment, the removal rate of the Chemical Oxygen Demand (COD) in the effluent of the biological aerated filter system which is the nanometer zero-valent metal lightweight porous spherical functional material is higher, and the analysis shows that the main reason for reducing the COD in the effluent is the physical adsorption effect of the nanometer zero-valent metal lightweight porous spherical functional material. The nanometer zero-valent metal light porous spherical functional material has the advantages of rough surface, large specific surface area, high porosity and a plurality of macroscopic pores, and provides a channel for the internal through air holes, so the adsorption capacity is strong. The COD removal rate of the effluent water at the 3 rd day is rapidly reduced and then shows a rising trend change, which indicates that the biological membrane starts to grow and has a biodegradation effect. After about 10 days, the COD of the effluent is relatively stable, and the removal rate reaches more than 85 percent, which indicates that the growth and reproduction speed of the heterotrophic microorganisms is relatively high.
The nanometer zero-valent metal light porous spherical functional material-biological aerated filter system enters a normal operation stage after membrane hanging is started for about 10 days and continuously operates for 7About a month, the indexes of the main pollutants COD and the ammonia nitrogen content (NH) in water3N), Total Phosphorus (TP), suspended matter (SS) were monitored continuously. The gas-water ratio is 1-10: l, hydraulic load 0.3m3/(m2.h)～0.8m3/(m2H) inflow of water COD, NH3The concentrations of-N, TN, TP, SS are respectively: 10mg/L-200mg/L, 5mg/L-50mg/L, 4mg/L-50mg/L, 0.5mg/L-2mg/L, 5mg/L-60 mg/L. The nano zero-valent metal light porous spherical functional material-biological aerated filter system is used for COD and NH3The removal rates of-N, TN, TP and SS are respectively 95-99%, 92-99%, 93-99%, 94-99% and 92-99%. The effluent concentrations of COD, NH3-N, TN, TP and SS in the nano zero-valent metal light porous spherical functional material-biological aerated filter system are respectively as follows: 1mg/L-5mg/L, 0.01mg/L-1mg/L, 1mg/L-5mg/L, 0.001mg/L-0.1mg/L, 1mg/L-10 mg/L. And the commercial filler-aeration biological filter system is used for treating COD and NH3The removal rates of-N, TN, TP and SS are respectively as follows: 40-48%, 30-57%, 20-59%, 20-49% and 30-55%. The effluent concentrations of COD, NH3-N, TN, TP and SS in the commercial filler-biological aerated filter system are respectively as follows: 50mg/L-100mg/L, 10mg/L-20mg/L, 10mg/L-25mg/L, 1mg/L-1.5mg/L, 20mg/L-40 mg/L.
Therefore, the invention applies the nanometer zero-valent metal light porous spherical functional material in the biological aerated filter, and has better effect on sewage treatment. The nanometer zero-valent metal light porous spherical functional material prepared by the invention has higher porosity, higher bioactivity and adsorption performance, can be applied to an aeration biological filter to exchange and adsorb pollutant ions in wastewater, can also be used as a microorganism carrier for microorganism propagation and growth so as to realize wastewater purification effect, and can be used as a nitrogen-phosphorus compound fertilizer for soilless culture of vegetables and fruits after the nanometer zero-valent metal light porous spherical functional material is saturated in adsorption.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (12)
1. A method for preparing a nanometer zero-valent metal light porous spherical functional material based on meteorites is characterized by comprising the following steps:
step S1, the meteorite powder is used as the raw material to prepare the nanometer zero-valent metal composite material through reduction and calcination;
step S2, mixing zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant to obtain a mixture;
step S3, taking the porous spherical polyethylene plastic particles as a framework, and uniformly adhering the mixture to the framework to prepare the zeolite-based light porous spherical functional material;
and step S4, uniformly spraying the nano zero-valent metal composite material on the zeolite-based light porous spherical functional material to obtain the nano zero-valent metal light porous spherical functional material.
2. The method for preparing a nano zero-valent metal lightweight porous spherical functional material based on meteorites according to claim 1, wherein the nano zero-valent metal composite material in step S1 is obtained by reduction calcination of the meteorite powder in hydrogen or carbon monoxide atmosphere.
3. The method for preparing nano zero-valent metal lightweight porous spherical functional material based on meteorite according to claim 2, wherein the calcination temperature in the atmosphere of hydrogen or carbon monoxide in the step S1 is 400-900 ℃, and the calcination time is 2-5 h.
4. The method for preparing nano zero-valent metal lightweight porous spherical functional material based on meteorites as claimed in claim 1, wherein the particle size of the meteorite powder in step S1 is less than 0.0374 mm.
5. The method for preparing nano zero-valent metal lightweight porous spherical functional material based on meteorites as claimed in claim 1, wherein the mixture is adhered in the pore structure of the polyethylene porous spherical plastic granules under the mechanical action of a mechanical roller in step S3.
6. The method for preparing nano zero-valent metal lightweight porous spherical functional material based on meteorites as claimed in claim 5, wherein the step S3 specifically comprises the following steps:
step S31, putting the porous spherical polyethylene plastic particles into a mechanical roller, and uniformly scattering the mixture on the porous spherical polyethylene plastic particles to obtain a porous functional material;
step S32, uniformly spraying water into the porous functional material to enable the porous functional material to become spherical particle material under the action of the roller;
and step S33, naturally curing the granular material to obtain the zeolite-based light porous spherical functional material.
7. The method for preparing a nano zero-valent metal lightweight porous spherical functional material based on meteorites as claimed in claim 1, wherein the mass ratio of the zeolite, the cement, the quicklime, the aluminum powder and the gypsum in step S2 is 50% -60%: 10% -30%: 1% -15%: 0.1% -2%: 1 to 13 percent.
8. The nano zero-valent metal lightweight porous spherical functional material prepared by the method for preparing the nano zero-valent metal lightweight porous spherical functional material based on the merle as claimed in any one of claims 1 to 7.
9. The light porous spherical functional material of nanometer zero-valent metal according to claim 8, wherein the light porous spherical functional material of nanometer zero-valent metal has multi-level pores comprising micropores of 1nm to 5nm, mesopores of 10nm to 50nm, and macropores of 50nm to 100 nm.
10. The light-weight porous spherical functional nano zero-valent metal material according to claim 8, wherein the porosity of the light-weight porous spherical functional nano zero-valent metal material is 90-99%.
11. The light porous spherical functional material of claim 8, wherein the specific surface area of the light porous spherical functional material of the nano zero-valent metal is 110-250m2/g。
12. Use of the light porous spherical functional nano zero-valent metal material as recited in claim 8 in a biological aerated filter.
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