CN110734128A - nanometer zero-valent metal light porous spherical functional material prepared based on meteorite, and preparation method and application thereof - Google Patents

nanometer zero-valent metal light porous spherical functional material prepared based on meteorite, and preparation method and application thereof Download PDF

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CN110734128A
CN110734128A CN201911075969.4A CN201911075969A CN110734128A CN 110734128 A CN110734128 A CN 110734128A CN 201911075969 A CN201911075969 A CN 201911075969A CN 110734128 A CN110734128 A CN 110734128A
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CN110734128B (en
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鲍腾
金杰
吴克
王晓飞
卫新来
张勇
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Hefei University
Hefei College
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention provides nanometer zero-valent metal light porous spherical functional materials prepared based on meteorites, a preparation method and application thereof, wherein the preparation method of the nanometer zero-valent metal light porous spherical functional materials comprises the steps of S1, preparing nanometer zero-valent metal composite materials by taking meteorite powder as a raw material through reduction and calcination, S2, mixing zeolite, cement, quicklime, aluminum powder, gypsum and a surfactant to obtain a mixture, S3, taking polyethylene porous spherical plastic particles as a framework, uniformly adhering the mixture to the framework to prepare zeolite-based light porous spherical functional materials, and S4, uniformly spraying the nanometer zero-valent metal composite materials on the zeolite-based light porous spherical functional materials to obtain the nanometer zero-valent metal light porous spherical functional materials.

Description

nanometer zero-valent metal light porous spherical functional material prepared based on meteorite, and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to light porous spherical nano zero-valent metal functional materials prepared based on meteorites, and a preparation method and application thereof.
Background
Phosphorus is which is indispensable nutrient for human survival, is mainly stored in the crust and exists in the form of phosphorus ore, and is non-metal mineral resources which are difficult to regenerate, the phosphorus flows in a straight line form of land → sea on the earth, more than 80 percent of phosphorus extracted from the phosphorus ore is used for producing phosphorus fertilizer, more than 50 percent of phosphorus in the phosphorus fertilizer which is not absorbed by crops can form surface runoff due to rain wash, the phosphorus which is not absorbed by human and animals in food enters surface water along with excrement under the condition of no sewage treatment, and finally the phosphorus enters the sea along with the natural law of 'river streak and open to the sea', except for excrement and excrement of sea birds on the land and marine products caught by the human sea, the phosphorus flowing into the sea is difficult to return to the land in the geological evolution period which can be hit by the human, therefore, phosphorus, coal, petroleum and the like belong to non-renewable 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. The data of the national statistical bureau show that the yield of the phosphate fertilizer reaches 970 multiplied by 10 in 20154t·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 phosphorite with super large and high quality (only can be directly used for producing high-concentration phosphorus compound fertilizer without mineral dressing) is discovered in the Guizhou Yang 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) The quantity of the basic reserves is only half of that of the basic 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 phenomenon of 'phosphorus crisis' comes with the phosphorite reserves.
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 rapid water supply filter, and integrates the characteristics of aeration, high filter speed, suspended matter interception, regular back flushing and the like in a body.
In the current application research of the biological aerated filter filler, most of the research focuses on the removal of phosphorus, but does not relate to the recovery of phosphorus, so that fillers are needed to realize the removal of nitrogen and the recovery of phosphorus simultaneously in the biological aerated filter reaction.
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 aspects of the above problems, the present invention provides methods for preparing a nano zerovalent metal lightweight porous spherical functional 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 hydrogen or carbon oxide atmosphere.
Optionally, the calcination temperature of the calcination in the hydrogen or carbon oxide atmosphere in the step S1 is 400 ℃ to 900 ℃, and the calcination time is 2h to 5 h.
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 nanometer zeroth order metal lightweight porous spherical functional materials prepared by the method for preparing the nanometer zeroth order metal lightweight porous spherical functional materials based on the merle in any .
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 nano zero-valent metal light porous spherical functional materials 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 methods for preparing nanometer zero-valent metal lightweight porous spherical functional materials 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 introduced into reducing atmosphere to be calcined to obtain the nanometer zero-valent metal composite material with higher activity, wherein the reducing atmosphere is hydrogen or carbon oxide, the calcining temperature of the reducing calcination is 400-900 ℃, and the calcining time is 2-5 h.
, the meteorite pretreatment process includes crushing meteorite to particle size less than 0.0374mm at normal temperature, mixing the meteorite with particle size less than 0.0374mm with alcohol, dispersing and stoving to obtain meteorite powder.
The meteorites are small solid fragments derived from the asteroid or comet, originating in the outer space, having an effect on both the earth's surface and the organism, called meteorites before they impact the earth's surface, ranging in size from small to very large, when meteorites enter the earth's atmosphere, they rise in temperature and glow due to friction, pressure, and the chemical action of gases in the atmosphere, thus forming meteorites, including the fireball, also called the jet.
The meteorite mainly comprises transition metals such as iron, nickel, manganese, arsenic, molybdenum, zirconium, niobium, ruthenium, rhodium, silver, cadmium, indium, cobalt, palladium, tin and antimony, because the meteorite contains a large amount of transition metals, the transition metal oxide has the following properties that a d electron layer of metal cations in the transition metal oxide volatilizes electrons or abstracts electrons and has stronger redox performance, the transition metal oxide has semiconductor properties, inner valence orbits and external orbits of the metal ions in the transition metal oxide can be split, the transition metal oxide and the transition metals can be used as redox reaction catalysts, the former has strong heat resistance and toxicity resistance and photosensitive, thermosensitive and impurity sensitivity and is more favorable for the performance regulation of the catalysts, so that the application is more universal, and the transition metals such as Fe and Co can form stronger synergistic action with Ni metal and also can obviously improve the catalytic activity of the Ni-based catalysts.
The nanometer zero-valent metal composite material prepared by taking meteorite as a raw material has main phases comprising nanometer zero-valent iron, nanometer zero-valent nickel, nanometer zero-valent copper and nanometer rare metals.
Therefore, the activity of the nano zero-valent metal composite metal can be enhanced by the multi-component composite material in the aspect, and the metals in the composition of the nano zero-valent metal composite material in the aspect can play a synergistic role, so that the speed and the selectivity of the nano zero-valent metal composite metal participating in the reduction reaction are improved.
, mixing the zeolite, cement, aluminum powder, calcium lime and gypsum according to mass percent to obtain a mixture, wherein the common Portland cement accounts for 10-30%, the zeolite accounts for 50-60%, the calcium lime accounts for 1-15%, the gypsum accounts for 1-13%, and the aluminum powder accounts for 0.1-2%.
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.
, 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, which 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; 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.
, the invention sprays the nanometer zero-valent metal composite material on the zeolite light porous spherical functional material 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 nanometer zero-valent metal light porous spherical functional material has the functions of adsorbing ammonia nitrogen in water, is an efficient microorganism carrier material, efficiently and synchronously recovering phosphorus and removing nitrogen, and also has the function of adsorbing various organic pollutants in water, wherein nanometer iron in the nanometer 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 reduced into ammonia nitrogen in step , 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 to reduce the reaction time and accelerate the denitrification reaction rate, and the nanometer zero-valent metal light porous spherical functional material comprises a porous structure composite porous material and a high-activity nanometer zero-valent metal composite material, the nanometer zero-valent metal light porous spherical functional material can form a multi-metal system, and the metals can perform a synergistic effect in a catalytic reaction to improve the catalytic degradation efficiency, in addition, the nanometer 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 microorganism load, is beneficial to degradation of the microorganisms to pollutants, and ensures thorough denitrification reaction due to anaerobic conditions formed by the structure of the material, thereby improving the removal effect of nitrate nitrogen by steps.
The nanometer zero-valent metal lightweight porous spherical functional material has high open porosity, so that various microorganisms can be attached to the outer surface and the inner part of the nanometer zero-valent metal lightweight porous spherical functional material, and the microorganisms form redox sub-bands on the outer surface and the inner part of the nanometer zero-valent metal lightweight porous spherical functional material and have the functions of oxidizing ammonia nitrogen and denitrifying denitrification.
Example
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.
water is evenly sprayed into the porous functional material to enable the porous functional material to be spherical under the action of a roller, and the spherical porous functional material is naturally cured for 20 days to prepare the zeolite-based light 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:
Figure BDA0002262451680000131
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:
Figure BDA0002262451680000141
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:
Figure BDA0002262451680000171
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 starts to form a film after about 10 days, enters a normal operation stage, continuously operates for about 7 months, and has indexes (NH) on main pollutants COD and ammonia nitrogen content 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, method for preparing nanometer zero-valent metal lightweight porous spherical functional material based on meteorite, which 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 oxide 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 of calcination in hydrogen or carbon oxide atmosphere in 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, light porous spherical nano-zero valent metallic functional materials prepared by the method for preparing light porous spherical nano-zero valent metallic functional materials based on merle as claimed in any of claims 1-7.
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 material of nanometer zero-valent metal as claimed in claim 8 in biological aerated filter.
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