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CN114471491A - Charcoal-loaded carbon aerogel nano-microsphere as well as preparation method and application thereof - Google Patents

Charcoal-loaded carbon aerogel nano-microsphere as well as preparation method and application thereof Download PDF

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CN114471491A
CN114471491A CN202111624344.6A CN202111624344A CN114471491A CN 114471491 A CN114471491 A CN 114471491A CN 202111624344 A CN202111624344 A CN 202111624344A CN 114471491 A CN114471491 A CN 114471491A
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侯浩波
李嘉豪
曾天宇
李安
罗腾
游以文
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Institute Of Resources And Environmental Technology Wuhan University Zhaoqing
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091Preparation of aerogels, e.g. xerogels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016Particle form
    • B01J20/28021Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/04Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases

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Abstract

The invention discloses a charcoal-loaded aerogel nano-microsphere and a preparation method and application thereof. And (2) obtaining the nano organogel microspheres by adopting an emulsion polymerization method, uniformly mixing the nano organogel microspheres and biomass raw material powder in a solvent medium, carrying out solid-liquid separation, and drying and carbonizing the solid mixture to obtain the biochar loaded carbon aerogel nanoparticles. The preparation method has the advantages of simple conditions, low equipment investment and operation cost and the like, and the obtained charcoal-loaded carbon aerogel nano-microspheres are used for repairing the soil polluted by heavy metals such as lead, cadmium, zinc and the like, have the characteristics of high heavy metal passivation efficiency, good biocompatibility, low use cost and the like, and have good industrial application prospects.

Description

Charcoal-loaded carbon aerogel nano-microsphere as well as preparation method and application thereof
Technical Field
The invention relates to a soil improvement material, in particular to a charcoal-loaded aerogel nano-microsphere, a preparation method of the charcoal-loaded aerogel nano-microsphere and application of the charcoal-loaded aerogel nano-microsphere as a heavy metal passivator in heavy metal contaminated soil, and belongs to the technical field of heavy metal contaminated soil improvement.
Background
Biochar is widely applied to improvement of farming soil, water and fertilizer holding performance of the farming soil can be improved, cation exchange capacity is increased, the pH value of the soil is increased, and the bioavailability of heavy metal in the soil is reduced by adsorption and precipitation of abundant pore structures and abundant carbonate substances, so that the biochar is used for repairing some heavy metal fields with low pollution degrees, and the biochar is limited in passivation capacity due to the fact that the biochar is limited by raw materials and pyrolysis temperature, and is independently added to serve as a soil repairing material for heavy metal contaminated fields with high concentration.
The microspherical aerogel is also called aerogel microspheres and is also called a microaerogel, is a special new material, is constructed by a nanoscale material, has a micron-sized size (usually between 1 and 1000 mu m), and also has a three-dimensional network porous structure as the macro massive aerogel. The aerogel is prepared into aerogel microspheres, so that the potential application range of the aerogel can be expanded, such as superabsorbents, medicine/catalyst carriers, functional composite particles, permeable membranes and the like. This is due to the fact that aerogel microspheres have a range of superior properties compared to aerogel blocks, such as: as a catalyst carrier, the catalyst has larger specific surface area and can provide more active reaction centers; as a filler, the resin composition has good fluidity, is easy to uniformly disperse, and is not easy to cause stress concentration.
Chinese patent (CN112892483A) discloses a nitrogen-doped carbon aerogel nano-microsphere and a preparation method and application thereof, the prepared nano-scale nitrogen-doped carbon aerogel microsphere has good adsorption capacity on heavy metals in a water solution, but due to the nano-size of the nano-scale nitrogen-doped carbon aerogel microsphere, the nano-scale nitrogen-doped carbon aerogel microsphere is easy to rapidly run off along with rainwater, surface runoff and the like in soil and has aggregation to a certain degree, so that the application of the nano-scale nitrogen-doped carbon aerogel microsphere in heavy metal contaminated soil remediation is limited.
Disclosure of Invention
Aiming at the defects that the existing biochar heavy metal passivation material is low in passivation efficiency on high-concentration heavy metal, and carbon aerogel microspheres with high passivation rate on heavy metal are easy to quickly run off along with rainwater, surface runoff and the like in a soil medium and agglomerate to a certain extent, the invention aims to provide the biochar-loaded carbon aerogel nanoparticles with a developed pore structure, a large specific surface area and a region-limited effect.
The second purpose of the invention is to provide a preparation method of the biochar-loaded carbon aerogel nano microsphere soil passivator, which is simple in process, low in cost and beneficial to large-scale production.
The invention also aims to provide the application of the charcoal-loaded aerogel nano-microspheres in the remediation of the heavy metal contaminated soil, the passivator can passivate the heavy metal in the contaminated site, has an improvement effect on the soil, and can achieve the purpose of remediation of the contaminated site.
In order to achieve the technical purpose, the invention provides a preparation method of charcoal-loaded aerogel nano-microspheres, which comprises the steps of obtaining nano-organogel microspheres by adopting an emulsion polymerization method, uniformly mixing the nano-organogel microspheres and biomass raw material powder in a solvent medium, carrying out solid-liquid separation, and drying and carbonizing a solid mixture to obtain the charcoal-loaded aerogel nano-microspheres.
The key point of the technical scheme of the invention is that the nano organogel microspheres are used for mixing and pyrolyzing with biomass raw materials, active functional groups on the surfaces of the nano organogel microspheres are chemically combined with functional groups of the biomass raw materials, so that the nano organogel microspheres are stably bonded in macroscopic pores of the biomass raw materials, the carbon aerogel nanoparticles are formed after high-temperature carbonization and stably dispersed and loaded in pores of biomass carbon aerogel, the carbon aerogel nanoparticles are used as functional particles with high adsorption activity on heavy metals, are fully dispersed and stably loaded, can expose more heavy metal adsorption active sites, and overcome the defects that the carbon aerogel nanoparticles are easy to agglomerate in the using process and have poor stability and are easy to lose, and the biomass carbon is used as a carrier material and has a certain heavy metal adsorption capacity, the adsorption effect of the carbon aerogel nano-microspheres on heavy metals in soil can be synergistically enhanced, and meanwhile, the biomass carbon material has good soil improvement effects such as water retention and fertilizer retention on soil.
As a preferred scheme, the biomass raw material comprises at least one of straw, rice hull, peanut shell and waste wood chips. The biomass is a common agricultural and forestry solid waste raw material, and can greatly reduce the production cost of the charcoal-loaded aerogel nano-microspheres.
As a preferable scheme, the nano organogel microspheres are nano phenolic resin organogel microspheres or nano organic amine-phenolic resin organogel microspheres. The nano organogel microspheres can be phenolic resin polymers or phenolic resins modified by nitrogen source doping, and are preferably nano organic amine-phenolic resin organogel microspheres, and the adsorption capacity to heavy metals can be improved by introducing heteroatom nitrogen.
As a preferable scheme, the mass percentage of the nano organogel microspheres to the biomass raw material powder is 0.5-20% to 80-99.5%, and more preferably 1-5% to 95-99%. When the proportion of the nano microspheres is too high, the biochar carrier cannot provide enough macro pores for the nano microspheres, so that the confinement effect is difficult to achieve, and the material cost is high; when the proportion of the nano microspheres is too low, the macroscopic pore utilization degree of the carrier is low, and the effect of improving the performance of the biochar is relatively poor.
As a preferable scheme, the total mass of the nano organogel microspheres and the biomass raw material powder is 1-60% of the mass of the solvent medium; more preferably 30 to 60%. By adopting a solvent medium with a proper proportion, the nano organogel microspheres and the biomass raw material powder are uniformly mixed.
As a preferred embodiment, the solvent medium is at least one of water, ethanol and methanol. The preferable solvent medium can improve the dispersion effect on the nano organogel microspheres and the wettability of the biomass raw material powder, and is beneficial to the dispersion loading of the nano organogel microspheres on the biomass raw material.
As a preferred scheme, the blending condition is as follows: the temperature is 15-90 ℃, the stirring speed is 10-600 r/min, and the time is 8-72 h. Preferably, the temperature is 25-45 ℃. The reaction of the active functional groups on the surface of the nano organogel microspheres and the active functional groups on the surface of the biomass raw material can be realized under the preferable uniform mixing condition, so that the nano organogel microspheres are stably bonded in the macroscopic pores of the biomass raw material.
As a preferable embodiment, the carbonization conditions are as follows: and preserving the heat for 1-24 hours at the temperature of 300-1200 ℃ in a protective atmosphere. The protective atmosphere is generally an inert atmosphere, and an inert atmosphere such as nitrogen or argon can be selected. The reaction temperature is preferably 600-900 ℃, and the reaction time is preferably 1-6 h. The carbonization temperature has obvious influence on the abundance of functional groups on the surface of the material and the pore structure of the material, when the temperature is lower, the precursor of the material is not completely pyrolyzed, the specific surface area is relatively smaller, the number of micropores is less, and more surface active functional groups are reserved; when the carbonization temperature is higher, the passivation material with larger specific surface area is easy to obtain, and simultaneously has richer micropore structures, and the number of surface active functional groups is reduced. Therefore, in order to obtain the charcoal-loaded aerogel nano-microspheres with better comprehensive performance, the optimal carbonization condition range needs to be controlled.
Preferably, the drying is freeze drying, vacuum drying, supercritical drying, or normal temperature drying, and preferably normal temperature drying or vacuum drying.
The invention also provides a charcoal-loaded carbon aerogel nano-microsphere which is obtained by the preparation method. The charcoal-loaded carbon aerogel nano-microspheres take the charcoal as a carrier, and the charcoal aerogel nano-microspheres are uniformly dispersed and stably loaded in the macro pores of the charcoal.
As a preferable scheme, the specific surface area of the charcoal-loaded aerogel nano-microspheres is 40-150 m2(ii)/g, the average pore diameter is 5-40 nm. Further preferably, the specific surface area is 70 to 120m2(ii)/g, the average pore diameter is 8-20 nm.
The invention also provides application of the charcoal-loaded aerogel nano-microsphere as a heavy metal passivator for repairing heavy metal contaminated soil.
As a preferable scheme, the doping proportion of the charcoal-loaded aerogel nano-microspheres in the heavy metal contaminated soil is not higher than 5%; more preferably 0.5 to 4%, and still more preferably 1 to 3%.
The preparation method of the nano organogel microsphere comprises the following steps: dissolving a phenolic compound (or the phenolic compound and a polyamine compound) in an aldehyde-water mixed solution to obtain a water phase; mixing the water phase with a surfactant-containing water-insoluble oil phase, carrying out polymerization reaction under the condition of gradient stirring from fast to slow, and after the polymerization reaction is finished, carrying out centrifugal separation to obtain the water-soluble oil-based polymer. The phenolic compound comprises phenol and/or resorcinol. The amine compound comprises at least one of melamine, diethylenetriamine, triethylene tetramine and hexamethylene tetramine. The aldehyde-water mixed solution is a water solution of formaldehyde and/or furfural. The mass of the polyamine compound is 0.5-20% of the total mass of the phenolic compound, the aldehyde and the polyamine compound; more preferably 1% to 7%. The mass ratio of the phenolic compound to the aldehyde is 10: 1-1: 10; more preferably 3:1 to 1: 3. The total mass of the phenolic compound, the aldehyde and the polyamine compound is 1-60% of the mass of the water phase; more preferably 30 to 60%. The water-insoluble oil phase is at least one of cyclohexane, petroleum ether or peanut oil. The surfactant is span40 and/or span 80. The mass ratio of the surfactant to the water-insoluble oil phase is 1: 1-1: 20; more preferably 1:8 to 1: 12. The volume ratio of the water phase to the surfactant-containing water-insoluble oil phase is 10: 1-1: 10; more preferably 5:1 to 1: 1. The conditions of the polymerization reaction are as follows: firstly, reacting for 1-20 min at the temperature of 25-90 ℃ under the stirring condition of 600-2000 r/min, and then reacting for 8-72 h at the temperature of 25-90 ℃ under the stirring condition of 10-600 r/min; further preferred polymerization conditions are: the reaction is carried out for 3-12 min at the temperature of 45-65 ℃ under the stirring condition of 800-1200 r/min, and then the reaction is carried out for 12-36 h at the temperature of 45-65 ℃ under the stirring condition of 200-500 r/min.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the preparation method of the charcoal-loaded carbon aerogel nano-microsphere provided by the invention is simple in process, free of harmful waste, mild in reaction condition and suitable for large-scale production of passivation materials.
2. The charcoal-loaded carbon aerogel nano-microspheres provided by the invention are formed by uniformly dispersing and stably loading the carbon aerogel nano-microspheres in macroscopic pores of a biomass charcoal material, greatly improve the specific surface area, enrich the pore structure and show better heavy metal adsorption and passivation capabilities by compounding the carbon aerogel nano-microspheres and the macroscopic pores of the biomass charcoal material.
3. The biochar-loaded carbon aerogel nano-microspheres provided by the invention are used for heavy metal pollution remediation, can effectively passivate heavy metals in heavy metal polluted soil for a long time, have a certain improvement effect on the soil, and cannot damage the soil structure, and meanwhile, the biochar-loaded carbon aerogel nano-microspheres are simple in use method, small in addition amount in the heavy metal polluted soil, low in cost compared with aerogel microspheres, and beneficial to industrial application.
Drawings
FIG. 1 is an SEM image of a composite prepared in example 1: WBC900(a), (b); BNCA-1-900 (c); (d) (ii) a BNCA-2-900(e), (f).
FIG. 2 is an infrared spectrum of the BC, ONCA, WBC600, WBC900, BNCA-2-600, and BNCA-2-900 prepared in example 1.
Fig. 3 is a graph showing the leaching concentrations of various heavy metals in soil samples repaired with the composite material prepared in example 1: (a) pb, (b) Zn, and (c) Cd.
FIG. 4 is a graph of the morphological distribution of various heavy metals in the soil sample repaired with the composite material prepared in example 1: (a) pb, (b) Zn, and (c) Cd.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the organic aerogel microspheres comprises the following steps:
dissolving Resorcinol (Resorcinol, R) and a certain amount of Melamine (Melamine, M) in water, adding a certain proportion of formaldehyde solution according to the molar ratio of R to formaldehyde (F) of 1:2 and the molar ratio of M to F of 1:3, adding a proper amount of sodium carbonate (about 1% of the mass of R) as a catalyst, and stirring at room temperature until the sodium carbonate is completely dissolved. Uniformly mixing the R-M-F mixed solution with an oil phase (the volume ratio of a cyclohexane-oleophylic neutral emulsifier (Span-80) mixed solution) in a ratio of 1:3, pouring the mixture into a three-necked bottle, emulsifying at room temperature at a stirring speed of 1000R/min for 10min, ensuring the flow and uniformity of the system at a certain stirring speed (300R/min), performing polymerization reaction at 60 ℃ for 24h, gradually precipitating a brown yellow solid, and washing and drying with alcohol to obtain the final product.
The preparation method of the charcoal-loaded aerogel microsphere composite material comprises the following steps:
mixing organic aerogel microspheres with screened wheat straws according to a mass ratio of (5% and 10%), adding a proper amount of distilled water, stirring for 24 hours to ensure that the organic aerogel microspheres and the screened wheat straws are uniformly mixed, centrifuging the mixture, taking solid components, drying at room temperature, and heating to 600-900 ℃ (99.999% purity and 30cm flow rate) in an argon atmosphere in a tubular furnace3Min), increasing/decreasing temperature during heating and cooling at a constant rate of 10 ℃/min. Treating at a preset temperature for 2 hours, and respectively naming the products as BNCA-1-600, BNCA-2-600, BNCA-1-900 and BNCA-2-900 according to the adding amount of the organic aerogel microspheres and the highest temperature of heating. In addition, two non-aerogel containing biochar, WBC600 and WBC900, were prepared under the same conditions (5% and 10%, respectively).
The performance experiment of the composite material for adsorbing heavy metal comprises the following steps: carrying out isothermal adsorption experiments within the concentration range of 50-400 mg/L of heavy metal ions. Use ofPb(NO3)2、Zn(NO3)2And Cd (NO)3)2A simulated adsorption solution was prepared. 10mg of the adsorbent and 10mL of the simulated solution were placed in a 50mL centrifuge tube at 25 ℃ and pH 6, and adsorption was continued at 250rpm/min for 24 h.
The passivation effect of different materials on heavy metals in a soil sample and the change rule of influencing pH value, organic matters and the like are researched through a soil culture experiment. The mass ratio of the contaminated soil sample to the passivating material was set to 3% according to the level of heavy metal contamination in the soil sample, the estimated passivation capacity of the material and the repair cost, i.e. 100g of the dried soil sample and 3g of the passivating material were mixed completely in a sterilized 250mL glass bottle, then all the soil samples were continuously cultured in a constant temperature incubator for 120 days, the temperature was controlled at 20 ℃ ± 1 ℃, sterile distilled water was sprayed to ensure the soil moisture content was 20% ± 2%, and the control group received the same culture conditions without adding the passivating material, with the following results:
scanning electron microscopy is adopted to analyze the changes of the surface morphologies of the material before and after the biochar-loaded aerogel microspheres, WBC900, BNCA-1-900 and BNCA-2-900 are taken as examples respectively, and SEM spectra under different scales are shown in figure 1.
As shown in fig. 1(a) and (b), the biochar WBC900 without loaded aerogel microspheres shows a smooth macroporous structure, with a small amount of irregular particulate matter on the surface that may be ash of the biochar. As can be seen from fig. 1(e) and (f), a large number of nano-sized aerogel microspheres are loaded in the micro-sized macroscopic pore structure of the biochar, and the number of the nano-sized aerogel microspheres is relatively small at other positions, i.e., the carbon aerogel microspheres are taken as functional particles and are limited in the macroscopic pores of the biochar, so that a very interesting 'region confinement' phenomenon is formed, and the form provides rich reaction sites for the passivation of heavy metals, and simultaneously prevents the migration of the aerogel nanoparticles along with the liquid in the soil. The specific surface area and pore structure of several synthesized materials were determined by low temperature nitrogen adsorption, and the basic physicochemical properties of the six materials by organic element analysis are listed in the following table.
Physicochemical Properties of Table 16 materials
Figure BDA0003438504960000061
As can be seen from table 1, after the aerogel microspheres are loaded, the specific surface area of the biochar is obviously increased, and the average pore diameter is reduced, which indicates that the introduction of the aerogel microspheres provides a large amount of microporous structures; the results of the organic element analysis show that the loading of the aerogel increases the nitrogen content of the biochar, which may provide more active sites for the passivation of heavy metals. The raw materials and several materials are subjected to infrared spectrum characterization analysis on the organic functional groups on the surfaces, and the results are shown in the following chart.
As shown in FIG. 2, a comparison of the infrared spectra of straw as received (BC), organic nitrogen doped aerogel microspheres (ONCA), WBC600, WBC900, BNCA-2-600, and BNCA-2-900 can be seen at 1099, 1556, and 2918cm-1Corresponding to C-N, C ═ N, and-NH stretching vibrations, respectively, the C-N and C ═ N bonds of BNCA-2-600 and BNCA-2-900 remain during pyrolysis, while the-NH bond of BNCA-2-900 disappears due to thermal instability, as can be seen from the foregoing related description, the nitrogen-containing functional group can provide many active sites, thereby contributing to an increase in the adsorption capacity of BNCA-2-600 and BNCA-2-900 for heavy metals, thereby increasing their performance for passivation of heavy metals.
For the six materials as a whole, due to abundant active sites on the adsorbent, the adsorption of Pb (II), Zn (II) and Cd (II) ions is rapidly increased along with the increase of the original concentration, and the adsorption quantity is slowly increased and gradually reaches the maximum value along with the complete occupation of the active sites on the surface of the materials; comparing six materials, it is obvious that the adsorption capacity for three heavy metals shows a high consistency, i.e. the removal capacity for heavy metals is: BNCA-2-900 > BNCA-1-900 > BNCA-2-600 > BNCA-1-600 > WBC900 > WBC600, which shows that the higher the doping amount of the aerogel microspheres is, the stronger the heavy metal removal capability is at the same pyrolysis temperature, while the higher the pyrolysis temperature is, the stronger the heavy metal removal capability is at the same doping amount of the aerogel microspheres; the adsorption capacity of six materials for three heavy metals is Pb (II) > Cd (II) > Zn (II). The theoretical maximum adsorption capacities (qs) for Pb (II), Zn (II) and Cd (II) of BNCA-2-900, which has the strongest adsorption capacity, are 205.07, 105.56 and 137.89mg/g, while the relatively weakest WBC600 has 111.85, 50.48 and 61.68mg/g for Pb (II), Zn (II) and Cd (II), respectively.
As shown in fig. 3, in the blank sample without any passivation material, the leaching concentration of the heavy metal hardly changes, and this result shows that the soil itself has almost no purification capability for the heavy metal, and at the same time, no heavy metal morphological change occurs to cause the leaching concentration of the heavy metal to increase or decrease, and the pollution risk degree thereof is not improved or deteriorated under this condition. On the whole, for the samples added with various passivation materials, the reduction degree of the leaching concentration of the heavy metal is highly consistent with the adsorption capacity of the passivation material to various heavy metals, and the rule that the passivation rate of the heavy metal is BNCA-2-900 > BNCA-1-900 > BNCA-2-600 > BNCA-1-600 > WBC900 > WBC600 is also shown.
The morphological distribution of heavy metals in soil after 120 days of addition of various passivating materials was studied, and the results are shown in fig. 4.
As shown in FIG. 4, the forms of the three heavy metals in the soil in the original sample are mainly a residue state and a weak acid extractable state, after a culture period of 120 days, the changes of the forms of the heavy metals in the blank sample are almost negligible, the residue state (Pb: 61.48%, Zn: 56.31%, Cd: 70.99%) and the weak acid extractable state (Pb: 27.45%, Zn: 27.45%, Cd: 22.22%) are mainly used, although the residue state occupies most of the heavy metal forms, the unstable part still occupies a higher proportion, and based on the higher total heavy metal content in the soil sample, a large amount of heavy metals in the soil still have biological effectiveness. After 120 days of addition of the various passivating materials, the bioavailability of the heavy metals is significantly reduced, i.e. the ratio of the weak acid extractable and reducible fractions is reduced and the ratio of the oxidizable and residual fractions is increased. Wherein the ratio of the extractable state of the weak acid of Pb (II) is reduced most remarkably, the exchangeable state in BNCA-2-900 is reduced by 76.97%, followed by BNCA-1-900, BNCA-2-600, BNCA-1-600, WBC900 and WBC600 (72.23%, 67.49%, 58.01%, 48.53% and 29.57%), therefore, the influence of the added passivating material on the bioavailability of the heavy metal is basically consistent with the adsorption capacity of the passivating agent and the change rule of the leaching concentration of the passivating agent, BNCA-2-900 has larger adsorption capacity on Pb (II), Zn (II) and Cd (II), meanwhile, the compound has the best passivation capability in the soil culture process, the weak acid extraction states of the three heavy metals are respectively reduced by 76.97 percent, 64.46 percent and 38.23 percent, this indicates that the three heavy metals can be passivated to reduce their biotoxicity using BNCA-2-900. The addition of the passivating material to the soil may result in the conversion of the heavy metal from a readily leachable form to a chemically more stable form, thereby reducing the mobility and bioavailability of the heavy metal, presumably due to the increased pH of the soil and the binding of the heavy metal to the soluble SOM, in addition to the adsorption of the heavy metal by the passivating material itself. It has also been shown in previous studies that the mobility of pb (ii), zn (ii) and cd (ii) in soil decreases after application of different organic materials including biochar, and from the results of risk analysis it has been shown that the heavy metal risk decreases from medium to low risk after passivating soil with BNCA-2-900 for 120 days.

Claims (10)

1. A preparation method of charcoal-loaded carbon aerogel nano-microspheres is characterized by comprising the following steps: the preparation method comprises the steps of obtaining nano organogel microspheres by adopting an emulsion polymerization method, uniformly mixing the nano organogel microspheres and biomass raw material powder in a solvent medium, carrying out solid-liquid separation, and drying and carbonizing a solid mixture to obtain the nano organogel microspheres.
2. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1, which is characterized in that: the biomass raw material comprises at least one of straw, rice hull, peanut shell and waste wood chips.
3. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1, which is characterized in that: the nano organogel microspheres are nano phenolic resin organogel microspheres or nano organic amine-phenolic resin organogel microspheres.
4. The preparation method of the biochar-loaded carbon aerogel nano-microspheres according to any one of claims 1 to 3, which is characterized by comprising the following steps of: the mass percentage of the nano organogel microspheres to the biomass raw material powder is 0.5-20% and 80-99.5%.
5. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1, which is characterized in that: the total mass of the nano organogel microspheres and the biomass raw material powder is 1-60% of the mass of the solvent medium.
6. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1 or 5, wherein the preparation method comprises the following steps: the solvent medium is at least one of water, ethanol and methanol.
7. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1 or 5, wherein the preparation method comprises the following steps: the blending condition is as follows: the temperature is 15-90 ℃, the stirring speed is 10-600 r/min, and the time is 8-72 h.
8. The preparation method of the charcoal-loaded aerogel nano-microsphere according to claim 1, which is characterized in that: the carbonization treatment conditions are as follows: and preserving the heat for 1-24 hours at the temperature of 300-1200 ℃ in a protective atmosphere.
9. A charcoal-loaded carbon aerogel nano-microsphere is characterized in that: the preparation method of any one of claims 1 to 8.
10. The application of the charcoal-loaded aerogel nano-microsphere as claimed in claim 9, wherein the charcoal-loaded aerogel nano-microsphere comprises the following components: used as a heavy metal passivator for repairing heavy metal contaminated soil.
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