CN112774625B - Zirconia doped magnetic high-surface-activity carbon composite material, preparation method and application - Google Patents
Zirconia doped magnetic high-surface-activity carbon composite material, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental pollution restoration, and relates to a preparation method of a zirconia doped magnetic high-surface-activity biochar composite material. The preparation method of the zirconia doped magnetic high-surface-activity biochar composite material provided by the invention has the advantages that the arsenic content in environmental media such as water, soil and the like can be obviously reduced, the method has the characteristics of low cost, good effect, strong operability, repeated use, no secondary pollution and environment beautification, and the method can be popularized and applied in a large area.
Description
Technical Field
The invention belongs to the technical field of environmental pollution restoration, and relates to a zirconia doped magnetic high-surface-activity carbon composite material, and a preparation method and application thereof.
Background
Arsenic and its compounds are common environmental pollutants. In the processes of mining and smelting arsenic and arsenic-containing metal minerals, such as glass, pigment, raw materials, paper and pesticide production and coal combustion, a large amount of arsenic-containing waste residues, waste gas and waste water can be generated, and arsenic can enter soil, earth surface and underground water bodies through leaching, sedimentation, runoff and other processes, so that serious environmental pollution is caused, and even the arsenic can finally enter human bodies through water, soil, atmosphere, food and other ways to endanger human health. Arsenic in soil and water environments mainly exists in two forms of arsenate and arsenite, and is a pollutant with great harm to human health. Arsenic pollution of water and soil has become one of the major environmental problems facing the world.
At present, many methods for treating arsenic-polluted water and soil mainly comprise a biological repair technology, a physical repair technology and a chemical repair technology. Bioremediation techniques mainly include phytoremediation techniques and microbial remediation techniques, one of the key of which is to find super-enriched plants or microorganisms that have a specific ability to absorb and enrich arsenic, and the other key of which is how to rapidly reproduce super-enriched plants or microorganisms with a larger biomass. In view of the rare super-enriched plants or microorganism species with special arsenic absorbing and enriching capability, most of the super-enriched plants or microorganisms have special growth environments and small biomass, the repair period of the technology is long, the operability is not strong, and the harm of arsenic in water bodies to the environment and human bodies is difficult to be reduced rapidly and efficiently. Physical remediation technologies of arsenic-polluted water bodies include an electric enrichment separation method, a membrane separation method, an adsorbent addition method and the like, but the electric enrichment separation method and the membrane separation method require unique devices and have high energy consumption, and risk of secondary pollution. Physical remediation technologies of arsenic contaminated soil include an electric enrichment and separation method, a soil-alien method, and the like, but the electric enrichment and separation method requires a unique device and has high energy consumption, and the soil-alien method has large engineering amount and is difficult to remove arsenic pollutants from the soil. The chemical restoration method of the arsenic-polluted water body comprises technologies such as chemical precipitation, chemical extraction and the like, has a good restoration effect, but has limited removal capacity for trace pollutants. Chemical restoration techniques of arsenic-contaminated soil include chemical extraction methods, in-situ stabilization methods, and the like, but chemical extraction methods have serious damage to the soil structure so that the soil is at risk of losing productivity, and in-situ stabilization methods can reduce the bioavailability of arsenic in the soil in a short period of time but have the risk of re-releasing and activating at a later stage.
Compared with the prior art, the method for adding the adsorbent has the advantages of wide selection range of the adsorbent, low engineering cost, simple operation and running and the like, and has the capability of efficiently repairing the arsenic polluted water under the condition of having a proper adsorbent. At present, the treatment of the arsenic polluted water body is generally to directly add an adsorbent into the water body, and the arsenate, namely arsenite type pollutant in the water body is adsorbed on the adsorbent through the adsorption action of the adsorbent; similarly, for arsenic-contaminated soil, an adsorbent may be added thereto, and the arsenic-contaminated soil in the soil solution may be adsorbed on the adsorbent by adsorption. Clearly, the addition of the adsorbent to the body of water or soil only transfers arsenic contaminants to the adsorbent surface, and does not remove the arsenic contaminants from the body of water or soil at all; meanwhile, the stability of the adsorbent which is remained in the water body or the soil for a long time and is used for adsorbing the arsenic pollutant is unknown, and after a long time, along with the weakening of the binding force between the adsorbent and the pollutant, the arsenic pollutant is gradually desorbed so as to be returned to the water body or the soil environment again, and the environment and the human health are still threatened, so that the adsorbent has become a key factor for limiting the large-area popularization of the technology.
Zirconia of the formula ZrO 2 Is an amphoteric oxide, is environment-friendly and has stable chemical property. Zirconia, aluminum oxide, iron oxide and lanthanum oxide have similar functions, namely, the zirconia, aluminum oxide, iron oxide and lanthanum oxide can be subjected to surface complexation with phosphate radical, arsenate, arsenite and other pollutants in the environment to form a stable complex, so that the adsorption and enrichment of the pollutants in the environment medium on the zirconia surface are realized. Therefore, zirconia, aluminum oxide, iron oxide, lanthanum oxide, and the like are often used as adsorbents for the adsorption removal of arsenic and phosphorus-containing contaminants in environmental media such as water and soil. In general, in order to make the adsorbent have a high adsorption efficiency for contaminants, the adsorbent is often prepared as fine particles (nano-sized to micro-sized). However, the adsorbent after adsorbing the contaminants has a disadvantage in that it is difficult to separate from the environmental medium due to the small particles. Secondly, when the adsorbent particles are finer, for example, the particles have higher specific surface area and active adsorption sites from nano-size to micro-size, the adsorption capacity for pollutants can be obviously improved in theory, but the adsorbents with the fine particles can be seriously agglomerated in an aqueous phase environment, so that the adsorption process of the pollutants is blocked and even the adsorption capacity is not high. Therefore, the adsorbent with high surface activity is obtained, the agglomeration of the adsorbent is reduced in a particle dispersion mode as far as possible, and meanwhile, the easy separation characteristic of the adsorbent is improved, so that the adsorbent is key to efficiently removing environmental medium pollutants. Therefore, the adsorbent particles are purposefully loaded on a carrier which is easy to separate from water, so that the particle agglomeration of the adsorbent particles can be reduced, and the rapid separation can be realized.
Biochar is a type of refractory, stable, highly aromatic, carbon-rich solid porous material formed by pyrolysis of biomass such as animal and plant residues at temperatures of 350-700 ℃. The main elements contained in the biochar are C, H, O and the like, and have good environmental affinity. The biochar is used as a porous substance, has certain adsorption capacity and can be used as a carrier of fine particles. However, the conventional biochar material has lower porosity and stronger surface hydrophobicity, so that the affinity force of the conventional biochar material to hydrophilic carriers is lower, and the loading capacity of the conventional biochar material serving as a carrier is limited. How to prepare the highly porous and hydrophilic high-surface-activity biochar material is a key to promote the environmental application of the biochar material. Compared with common porous and hydrophilic mineral material carriers such as zeolite, diatomite and the like prepared by artificial synthesis or modification, the preparation process of the biochar is simple, the cost is low, the raw material sources are wide, and various wastes rich in organic matters, including common crop straws rich in organic matters, wood chips, leaves, branches, fruit peels, fruit residues, fur and scale of animals, bones and carcasses, kitchen wastes, sludge and the like, are mainly generated in the production process of agriculture, forestry, animal husbandry and fishery. Many researches show that the biochar is used as a carrier in terms of preparation cost, engineering application effect, subsequent residue treatment cost, potential environmental influence and the like, and has better environmental application potential than common high-porosity hydrophilic mineral material carriers such as zeolite, diatomite and the like prepared by artificial synthesis or modification.
The zirconia-doped biochar is prepared by loading zirconia fine particles on the biochar through a directional doping technology, so that the problems that the zirconia fine particles are easy to aggregate and have low adsorption efficiency in a liquid-phase environment medium system (in water and soil solution) can be solved, and the separation of the zirconia fine particles from the environment medium system can be promoted while the dispersibility of the zirconia fine particles is improved. However, if the zirconia doped biochar adsorbed with arsenic pollutants is to be removed rapidly from an environmental medium system, a certain easy-to-separate property needs to be given to the biochar material, otherwise, separation is difficult to be carried out by a common filter paper filtration mode, and if separation is carried out by a filter membrane filtration mode, engineering application cost is greatly increased. Therefore, the biochar material is considered to be loaded with magnetism, and after being added into a water body or soil solution to adsorb arsenic pollutants, the zirconia doped biochar is directly sucked out by using an external magnetic field, so that the arsenic pollutants are thoroughly removed from the water body and soil environment.
The biochar raw material, zirconia and iron solution can be prepared in a large quantity at low cost, the agricultural and forestry or domestic organic waste is utilized to prepare the magnetic biochar with high porosity and high surface hydrophilicity, the zirconia is loaded on the biochar through a directional doping technology, the zirconia doped magnetic high surface active carbon composite material is prepared, and the zirconia doped magnetic high surface active carbon composite material is used for removing arsenic pollutants in environmental media such as water, soil and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a zirconia doped magnetic high-surface-activity carbon composite material, which aims to solve the problems of poor adsorbent effect, difficult separation of the adsorbent and even secondary pollution caused by an adsorbent adding method in the existing arsenic polluted water treatment; the composite material can obviously reduce the arsenic content of environmental media such as water, soil and the like, has the characteristics of low cost, good effect, strong operability, repeated use, no secondary pollution and environment beautification, and can be popularized and applied in a large area.
The invention relates to a preparation method of a zirconia doped magnetic high-surface-activity carbon composite material, which is characterized in that organic matters and soluble ferric salt are mixed and pyrolyzed to introduce ferroferric oxide particles to obtain a magnetic biochar material, and zirconia fine particles are directionally doped and loaded on the magnetic biochar material to prepare the zirconia doped magnetic high-surface-activity biochar composite material with a porous core-shell structure.
Preferably, the method specifically comprises the following steps:
s101, mixing an organic matter with a soluble ferric salt solution, then sealing and placing for 12-24 hours, drying, continuously heating to 500-550 ℃ at a speed of 5-10 ℃/min under an inert atmosphere, pyrolyzing for 1-2 hours, and cooling to obtain a crude product of the magnetic biochar material;
the adding amount of iron ions in the soluble ferric salt solution is 8-10% of the total mass of the organic matters;
s102, adding a pore-forming agent into the crude magnetic biochar material, heating to 700-800 ℃ at a speed of 5-10 ℃/min under an inert atmosphere, pyrolyzing for 1-2 h, sequentially cooling, washing, drying and grinding, and then separating from the obtained solid product under the action of an externally applied magnetic field to obtain the magnetic biochar material with high surface activity;
and S103, after the high-surface-activity magnetic biochar material is dissolved, adding zirconium tetrachloride solution, stirring to form a homogeneous suspension, adding an alkaline solution with the same volume as that of the zirconium tetrachloride solution, standing, and sequentially washing and drying the obtained solid to obtain the zirconia-doped high-surface-activity magnetic biochar composite material.
Preferably, in S101, the soluble ferric salt solution is a ferric salt solution or a ferrous salt solution, or a mixed solution of ferric iron and ferrous iron in a molar ratio of 1:2;
the ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the ferrous salt is one or more of ferrous chloride, ferrous nitrate and ferrous sulfate.
Preferably, in S102, the pore-forming agent is one of sodium hydroxide, sodium bicarbonate, and sodium carbonate;
preferably, in S103, the concentration of the zirconium tetrachloride solution is 0.05-0.1 mol/L, and the adding amount of the zirconium tetrachloride solution is 20-40 mL.
Preferably, in S103, the high-surface-activity magnetic biochar material is dissolved according to 1g: 50-100 mL of the solvent is mixed with the solvent, and the solvent is absolute ethyl alcohol and deionized water according to the volume ratio of 1-2: 1, mixing the obtained solution;
the alkaline solution is concentrated ammonia water or sodium hydroxide solution with the concentration of 0.25-0.3 mol/L.
The invention also provides the zirconia doped magnetic high-surface-activity biochar composite material prepared by the preparation method.
The zirconia doped magnetic high-surface-activity biochar composite material can be used for removing arsenic-containing pollutants.
The invention also provides a regeneration method of the zirconia doped magnetic high-surface-activity biochar composite material, which comprises the following steps:
mixing the zirconia doped magnetic high-surface-activity biochar composite material adsorbed with arsenic pollutants with a desorption solution, and stirring for 4-6 hours;
the desorption solution is a mixed solution prepared by sodium carbonate and dipotassium hydrogen phosphate according to a molar ratio of 1:1, and the concentration of the sodium carbonate and the dipotassium hydrogen phosphate in the mixed solution is 0.1-0.5 mol/L.
Preferably, the repeated use times of the zirconia doped magnetic high-surface-activity biochar composite material regenerated by the method are 4-5 times.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, zirconia fine particles are loaded on a magnetic biochar material by a directional doping technology to prepare the zirconia doped magnetic biochar composite material with high surface activity, so that the problems of aggregation and low adsorption efficiency of the zirconia fine particles in a liquid phase system can be solved, the dispersibility of the zirconia fine particles is improved, and meanwhile, arsenic pollutants in an environment medium can be promoted to be in adsorption contact with the surfaces of the zirconia fine particles, so that the zirconia fine particles have better arsenic pollutant removal capability, and meanwhile, the loss of the zirconia fine particles can be effectively reduced; in addition, as magnetism is loaded, the zirconia doped high-surface-activity magnetic biochar composite material after arsenic pollutant adsorption can be thoroughly removed from the environment, and meanwhile, desorption and recycling can be performed;
2. the raw materials adopted by the invention are agriculture and forestry or domestic organic waste garbage (such as straw, wood dust, leaves, branches, animal fur and scale, residual rice steamed bread, vegetable and fruit peel and the like, and the domestic garbage containing metal, glass, stones, soil, plastic products and the like is not included), the daily yield is large, the organic matter content is high, the environment pollution is not easy to cause due to improper treatment, and the agriculture and forestry or domestic organic waste garbage is taken as the raw materials, and can be obtained in large quantity without additional cost;
3. the chemical reagents such as ferric chloride, ferric nitrate, ferrous chloride, ferrous nitrate, sodium hydroxide, sodium bicarbonate, absolute ethyl alcohol, ammonia water, zirconium tetrachloride and the like used in the invention have low cost, are green and pollution-free, and the material preparation process is simple and effective to operate;
4. the agriculture and forestry or domestic organic waste garbage is pyrolyzed to prepare the high-surface-activity magnetic biochar material with good adsorption capacity, so that the waste can be converted into resources with application value, the separation and collection performances are convenient, and the engineering application value is potential;
5. the invention has the advantages of high efficiency in removing arsenic pollutants in water and soil, low cost, good effect, strong operability, no secondary pollution, environment beautification and the like, and can be popularized and applied in a large area;
6. the zirconia doped high-surface-activity magnetic biochar composite material prepared by the invention has the characteristic of material recycling; after removing arsenic pollutants in the environment medium, the desorption treatment can be carried out by using a sodium carbonate-dipotassium hydrogen phosphate mixed desorption solution, so that the regeneration of the zirconia doped high-surface-activity magnetic biochar composite material is realized, and the material can be repeatedly used for 4-5 times;
7. the zirconia doped high-surface-activity magnetic biochar composite material prepared by the invention has the characteristics of green and pollution-free; in the regeneration treatment of the material, the used arsenic-containing sodium carbonate-dipotassium hydrogen phosphate mixed desorption solution can be added with water-soluble aluminum salt or ferric salt to form solid precipitate substances which can be used as mineral raw materials for recovering elements such as iron, zirconium, arsenic and the like or sending the mineral raw materials to a hazardous waste treatment center for treatment, so that secondary pollution to the environment is avoided; the zirconia doped high-surface-activity magnetic biochar composite material can be directly incinerated after being repeatedly used for a plurality of times in removing arsenic pollutants in an environmental medium, if the performance of the material does not meet the requirement, the material is invalid, the obtained solid residue contains iron, zirconium, arsenic and the like, can be used as mineral raw materials for recycling elements such as iron, zirconium, arsenic and the like or is sent to a hazardous waste treatment center for treatment, and secondary pollution to the environment is avoided.
Drawings
FIG. 1 is an X-ray crystal diffraction (XRD) spectrum of a zirconia doped magnetic high-surface-activity biochar composite material provided in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the zirconia doped magnetic high-surface-activity biochar composite material provided in example 1 of the present invention;
FIG. 3 is a graph showing the elemental composition distribution of micro-area X-ray fluorescence analysis (μ -XRF) of the zirconia doped magnetic high-surface-activity biochar composite provided in example 1 of the present invention;
FIG. 4 is a graph of regeneration efficiency of the zirconia doped magnetic high surface activity biochar composite material provided by the invention;
FIG. 5 is a graph of recycling efficiency of the zirconia doped magnetic high-surface-activity biochar composite material provided by the invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and specific embodiments.
Example 1
A preparation method of a zirconia doped magnetic high-surface-activity biochar composite material comprises the following steps:
s101, washing agriculture and forestry or living organic materials (such as straw, wood chip, leaf, branch, animal fur and scaly, residual rice steamed bread, vegetable and fruit peel, etc.), oven drying at 105deg.C, pulverizing, mixing with FeCl of equal volume 3 ·6H 2 O/FeCl 2 ·4H 2 Mixing the mixed solution of O fully, sealing, standing for 12h, drying at 105 ℃, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, heating to 500 ℃ with a gradient of 5 ℃/min under the inert condition, continuing pyrolysis for 2h, cooling to room temperature, and taking out to obtain a magnetic biochar crude product;
wherein FeCl 3 ·6H 2 O and FeCl 2 ·4H 2 The molar ratio of O is 2:1, and FeCl 3 ·6H 2 O/FeCl 2 ·4H 2 The iron element in the O mixed solution accounts for 8% of the total mass of the total organic material;
s102, mixing and fully grinding the obtained magnetic biochar coarse product with sodium hydroxide with equal mass, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, under an inert condition, setting a program, heating to 700 ℃ with a gradient of 5 ℃/min, continuing pyrolysis for 2 hours to obtain rich pore structures, cooling to room temperature, taking out, washing 3-4 times with deionized water, drying at 105 ℃, carefully grinding to a particle size of less than 2mm, and separating from a solid product with an external magnetic field (such as a magnet) to obtain a magnetic biochar material fine product with high surface activity;
s103, weighing 1g of the magnetic biochar material obtained in the step S102, adding 100mL of absolute ethyl alcohol-deionized water mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is equal to 2:1) into a 400mL beaker, adding 20mL of 0.05mol/L zirconium tetrachloride solution, continuously stirring for 2 hours to form a homogeneous suspension, obtaining zirconium (hydrogen) oxide, loading the zirconium (hydrogen) oxide into a porous carbon material, slowly adding 20mL of ammonia water dropwise, and stirring while dropwise adding to fully and uniformly mix the zirconium (hydrogen) oxide; and standing at 25 ℃ for 24 hours, collecting solid particles settled at the bottom of the beaker, flushing with deionized water for 3-4 times, and drying at 105 ℃ for 2 hours to obtain the zirconia doped magnetic high-surface-activity biochar composite material.
Example 2
A preparation method of a zirconia doped magnetic high-surface-activity biochar composite material comprises the following steps:
s101, washing agriculture and forestry or living organic materials (such as straw, wood chip, leaf, branch, animal fur and scaly, residual rice steamed bread, vegetable and fruit peel, etc.), oven drying at 105deg.C, pulverizing, mixing with FeCl of equal volume 3 ·6H 2 O/FeCl 2 ·4H 2 Mixing the mixed solution of O fully, sealing, standing for 12h, drying at 105 ℃, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, heating to 550 ℃ in a gradient of 10 ℃/min under the inert condition, continuing pyrolysis for 1h, cooling to room temperature, and taking out to obtain a magnetic biochar crude product;
wherein FeCl 3 ·6H 2 O and FeCl 2 ·4H 2 The molar ratio of O is 2:1, and FeCl 3 ·6H 2 O/FeCl 2 ·4H 2 The iron element in the O mixed solution accounts for 10% of the total mass of the total organic material;
s102, mixing the obtained magnetic biochar coarse product with sodium hydroxide with equal mass, fully grinding, filling the mixture into a porcelain crucible, compacting, transferring the porcelain crucible into a temperature-controlled muffle furnace, heating to 800 ℃ with a gradient of 10 ℃/min under an inert condition, continuously pyrolyzing for 1h, cooling to room temperature, taking out the mixture, flushing the mixture with deionized water for 3-4 times, drying the mixture at 105 ℃, carefully grinding the mixture until the particle size is smaller than 2mm, and separating the mixture from a solid product by using an external magnetic field (such as a magnet) to obtain a magnetic biochar material refined product with high surface activity;
s103, weighing 1g of the magnetic biochar material obtained in the step S102, adding 100mL of absolute ethyl alcohol-deionized water mixed solution (the volume ratio of the absolute ethyl alcohol to the deionized water is equal to 1-2:1) into a 400mL beaker, adding 20mL of 0.1mol/L zirconium tetrachloride solution, continuously stirring for 2 hours to form a homogeneous suspension, then slowly adding 20mL of ammonia water dropwise, and stirring while adding dropwise to fully and uniformly mix the solution; and standing at 25 ℃ for 24 hours, collecting solid particles settled at the bottom of the beaker, flushing with deionized water for 3-4 times, and drying at 105 ℃ for 2 hours to obtain the zirconia doped magnetic high-surface-activity biochar composite material.
Example 3
A preparation method of a zirconia doped magnetic high-surface-activity biochar composite material comprises the following steps:
s101, washing agriculture and forestry or living organic materials (such as straw, wood chip, leaf, branch, animal fur and scaly, residual rice steamed bread, vegetable and fruit peel, etc.), oven drying at 105deg.C, pulverizing, mixing with Fe with equal volume 2 (SO 4 ) 3 /Fe(NO 3 ) 2 Mixing the mixed solution fully, sealing, standing for 12h, drying at 105 ℃, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, heating to 500 ℃ with a gradient of 10 ℃/min under an inert condition, continuing pyrolysis for 1.5h, cooling to room temperature, and taking out to obtain a magnetic biochar crude product;
wherein Fe is 2 (SO 4 ) 3 With Fe (NO) 3 ) 2 Is 2:1, and Fe 2 (SO 4 ) 3 /Fe(NO 3 ) 2 The iron element in the mixed solution accounts for 9% of the total mass of the total organic material;
s102, mixing the obtained magnetic biochar coarse product with sodium carbonate of equal quality, fully grinding, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, setting a program, heating to 800 ℃ in a gradient manner of 5 ℃/min under an inert condition, continuing pyrolysis for 2 hours to obtain rich pore structures, cooling to room temperature, taking out, washing 3-4 times with deionized water, drying at 105 ℃, carefully grinding to a particle size of less than 2mm, and separating from a solid product by using an external magnetic field (such as a magnet) to obtain a magnetic biochar material fine product with high surface activity;
s103, weighing 1g of the magnetic biochar material obtained in the step S102, adding 50mL of absolute ethyl alcohol-deionized water mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is equal to 1:1) into a 400mL beaker, adding 20mL of 0.05mol/L zirconium tetrachloride solution, continuously stirring for 2 hours to form a homogeneous suspension, obtaining zirconium (hydrogen) oxide, loading the zirconium (hydrogen) oxide into a porous carbon material, slowly adding 20mL of 0.25mol/L sodium hydroxide solution dropwise, and stirring while dropwise adding to fully and uniformly mix the zirconium (hydrogen) oxide; and standing at 25 ℃ for 24 hours, collecting solid particles settled at the bottom of the beaker, flushing with deionized water for 3-4 times, and drying at 105 ℃ for 2 hours to obtain the zirconia doped magnetic high-surface-activity biochar composite material.
Example 4
A preparation method of a zirconia doped magnetic high-surface-activity biochar composite material comprises the following steps:
s101, washing agriculture and forestry or living organic materials (such as straw, wood chip, leaf, branch, animal fur and scaly, residual rice steamed bread, vegetable and fruit peel, etc.), oven drying at 105deg.C, pulverizing, mixing with Fe (NO) with equal volume 3 ) 2 Mixing the solution fully, sealing, standing for 12h, drying at 105 ℃, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, heating to 550 ℃ in a gradient manner of 5 ℃/min under the condition of oxygen deficiency (nitrogen or argon protection), continuing pyrolysis for 2h, cooling to room temperature, and taking out to obtain a magnetic biochar crude product;
wherein Fe (NO) 3 ) 2 The iron element in the solution accounts for 9% of the total mass of the total organic material;
s102, mixing the obtained magnetic biochar coarse product with sodium bicarbonate with equal mass, fully grinding, loading into a porcelain crucible, compacting, transferring into a temperature-controlled muffle furnace, under an inert condition, setting a program, heating to 750 ℃ in a gradient manner at 5 ℃/min, continuing pyrolysis for 2 hours to obtain rich pore structures, cooling to room temperature, taking out, washing 3-4 times with deionized water, drying at 105 ℃, carefully grinding to a particle size of less than 2mm, and separating from a solid product by using an external magnetic field (such as a magnet) to obtain a magnetic biochar material fine product with high surface activity;
s103, weighing 1g of the magnetic biochar material obtained in the step S102, adding 100mL of absolute ethyl alcohol-deionized water mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is equal to 2:1) into a 400mL beaker, adding 20mL of 0.1mol/L zirconium tetrachloride solution, continuously stirring for 2 hours to form a homogeneous suspension, obtaining zirconium (hydrogen) oxide, loading the zirconium (hydrogen) oxide into a porous carbon material, slowly adding 20mL of 0.3mol/L sodium hydroxide solution dropwise, and stirring while dropwise adding to fully and uniformly mix the zirconium (hydrogen) oxide; and standing at 25 ℃ for 24 hours, collecting solid particles settled at the bottom of the beaker, flushing with deionized water for 3-4 times, and drying at 105 ℃ for 2 hours to obtain the zirconia doped magnetic high-surface-activity biochar composite material.
Further X-ray crystallography (XRD, as in fig. 1) analysis of the zirconia doped magnetic high surface active biochar composite material obtained in example 1 revealed that magnetic ferroferric oxide crystals were incorporated into the biochar matrix.
The zirconia doped magnetic high-surface-activity biochar composite material obtained in the example 1 is found by scanning electron microscopy (SEM, as shown in figure 2) and micro-region X-ray fluorescence spectroscopy (mu-XRF, as shown in figure 3), zirconia particles (5-40 nm) in the zirconia doped biochar composite material are uniformly dispersed in the surface and pores of the biochar, and the prepared zirconia doped high-surface-activity magnetic biochar composite material is a carbonaceous composite material with a porous core-shell structure.
Since the zirconia doped magnetic high-surface-activity biochar composite materials prepared in example 1, example 2, example 3 and example 4 have substantially the same properties, the zirconia doped magnetic high-surface-activity biochar composite material prepared in example 1 is used as an example only to illustrate the removal effect of arsenic pollutants.
When removing arsenic pollutants in water, the obtained zirconia doped magnetic high-surface-activity biochar composite material is added into an arsenic polluted environment medium with the arsenic content lower than 5mg/L in a solid-liquid ratio of 0.1g/L, or is added into the arsenic polluted environment medium with the arsenic content between 5 and 25mg/L in a solid-liquid ratio of 0.5 g/L; for the environment medium with arsenic content higher than 25mg/L, the environment medium can be diluted to the concentration lower than 25mg/L, then the materials are added according to the adding amount, and then the materials are fully mixed for 6 to 12 hours, and the zirconia doped magnetic high-surface-activity biological carbon composite material is sucked out of the water body by an external magnetic field (such as a magnet). The material can realize the removal of more than 90% of arsenic pollutants in the water body (see table 1). If the arsenic content in the water is higher than the pollution concentration range, the adding amount of the zirconia doped magnetic high-surface-activity biochar composite material can be increased according to the actual arsenic content by referring to the table 1 so as to achieve the aim of removing arsenic pollutants.
TABLE 1 efficiency of arsenic removal from Water
When removing arsenic pollutants in polluted soil, air-drying an arsenic polluted soil sample (the arsenic content is between 15 and 40 mg/kg) and grinding until the particle size is smaller than 2mm, then mixing the arsenic polluted soil sample and water according to the mass-volume ratio of 1:2.5-5, placing the mixed sample into a polyethylene plastic bottle at room temperature, sealing a bottle mouth by a bottle cap with a soft rubber pad, performing anaerobic culture for 15 to 20 days, adding the zirconia-doped high-surface-activity magnetic carbon composite material according to the ratio of 3 to 5g/kg (the mass ratio of the zirconia-doped high-surface-activity magnetic carbon composite material to the soil sample), fully stirring for 6 to 12 hours, and magnetically separating the zirconia-doped high-surface-activity magnetic carbon composite material from the soil suspension by using an external magnetic field (such as a magnet), so that 30 to 60 percent of arsenic pollutants in the arsenic polluted soil can be removed (see table 2). If the arsenic content in the soil is higher than the pollution concentration range, the water consumption can be properly increased according to the actual arsenic content of the soil to dilute and then the carbon material is added, or the adding amount of the zirconia doped magnetic high-surface-activity biological carbon composite material is appropriately increased, so that the aim of removing arsenic pollutants is fulfilled.
TABLE 2 efficiency of arsenic removal from soil
The test research is carried out on the simulated arsenic-containing wastewater, the Shaanxi river water and the water sample of the Shaanxi river and the water sample of the Shaanxi river. Simulating the arsenic content of 1, 2.5 and 5mg/L of the polluted Shaanxi Wei river water; simulating polluted water of a water treatment system the arsenic content of the additive is 1 2.5 and 5mg/L; arsenic-containing wastewater was simulated as a series of 0.1, 1, 5, 10 and 25mg/L aqueous solutions of sodium arsenite prepared by adding sodium arsenite to tap water.
When removing arsenic pollutants in polluted water, 1 liter of wastewater with arsenic content of 1-5 mg/L and the simulated polluted wastewater are respectively adjusted to pH 3.0-5.0, and then 0.2g of zirconia doped magnetic high-surface-activity biochar composite material is respectively added; for the polluted water body with arsenic content higher than 5mg/L, regulating the pH to 3.0-5.0, and then adding 0.5g of zirconia doped magnetic high-surface-activity biochar composite material; fully stirring for 6-12 h, standing for 10min, and magnetically separating and recovering the biochar material from the solution by using a magnet.
The treated water was tested according to the environmental protection standard of the people's republic of China using the arsenic content detection method standard-cyanide generation-atomic fluorescence spectrometry (HJ/694-2014), and the results are shown in Table 3.
TABLE 3 results of arsenic removal from simulated contaminated water bodies
As can be seen from Table 3, the detection results of the river water and the lake water after treatment show that the arsenic content is lower than the limit value of the arsenic content in the national sanitary standard (GB 5749-2006) of the drinking water, and the arsenic content in the simulated arsenic-containing wastewater after treatment is lower than the limit value of the arsenic content specified by the national quality standard (HJ/3838-2002) of the surface water environment by 0.01 mg/L.
When arsenic pollutants in polluted soil are removed, respectively taking arsenic polluted soil samples of Shaanxi Yang Ling, shenzhen, hubei Yichang, neomeggu, gansu silver, hunan Chenzhou, sichuan Guangyuan, yunnan Kunming and the like for experiments. Early tests showed that the arsenic content of the arsenic contaminated soil samples of Shaanxi Yang Ling, shenzhen, hubei Yichang, nemongolian baotou, gansu silver, chenzhou, sichuan Guangyuan, yunnan Kunming and the like were 21.45 mg/kg, 28.26 mg/kg, 22.35 mg/kg, 18.52 mg/kg, 58.71 mg/kg, 19.64 mg/kg, 20.76 mg/kg and 37.93mg/kg, respectively.
The specific process for removing arsenic pollutants in the polluted soil comprises the following steps: the soil sample is naturally air-dried and then ground to the grain size smaller than 2mm, then 100g of soil sample is weighed and added into a polyethylene plastic bottle containing 300mL of distilled water, and then the mixture is stirred and mixed uniformly, anaerobic culture is carried out for 15-20 days at room temperature in a sealing way, 0.3-0.5 g of zirconia doped magnetic high-surface-activity biochar composite material is respectively added, and after full stirring is carried out for 6-12 h, the biochar material is magnetically separated from the soil suspension by using a magnet.
According to the environmental protection standard of the people's republic of China, the arsenic content in the soil suspension is detected by adopting a hydrochloric acid and nitric acid digestion-cyanide generation-atomic fluorescence method (GB/T22105-2008), and the detection result is shown in Table 4.
TABLE 4 results of arsenic removal from contaminated soil
| Contaminated soil source land | As content of original soil (mg/kg) | The adding amount is%g) | As content of treated soil (mg/kg) |
| Shanxi Yang Ling | 21.45 | 0.3 | 13.19 |
| Shenzhen (Shenzhen) | 28.26 | 0.4 | 10.74 |
| Hubei Yichang | 22.35 | 0.3 | 10.18 |
| Inner Mongolian head | 18.52 | 0.3 | 13.67 |
| Chenzhou Hunan | 19.64 | 0.3 | 9.79 |
| Sichuan Guangyuan | 20.76 | 0.3 | 9.92 |
| Yunnan Kunming | 37.93 | 0.5 | 13.73 |
| Gansu white silver | 58.71 | 0.5 | 21.15 |
| Gansu white silver | 58.71 | 0.8 | 14.07 |
As can be seen from Table 4, according to the above material usage method, when the added amount of the zirconia doped magnetic high-surface-activity biochar composite material is 0.3-0.5 g, the arsenic content in the processed arsenic contaminated soil samples such as Shanxi Yang Ling, shenzhen, hubei Yichang, neimeverpa, hunan Chenzhou, sichuan Guangyuan and Yunnan Kunming is lower than the primary standard of the arsenic content limit value of 15mg/kg specified in the soil environmental quality standard (GB/15618-2018); as the arsenic content in the Gansu silver polluted soil exceeds the range of 15-40 mg/kg, the adding amount of the zirconia doped magnetic high-surface-activity biochar composite material is increased to 0.8g as appropriate, and the arsenic content in the treated soil can be lower than the limit value specified by the soil environmental quality standard.
The experiment shows that the zirconia doped magnetic high-surface-activity biochar composite material prepared by introducing ferroferric oxide particles into agriculture and forestry or domestic organic waste through pyrolysis to endow magnetism and carrying out directional doping on zirconia fine particles has obvious effects on adsorbing arsenic pollutants in arsenic-containing wastewater and arsenic-polluted soil, and can efficiently remove the arsenic pollutants in environmental media.
In order to explore the recycling of the zirconia-doped magnetic high-surface-activity biochar composite material, the application cost of removing arsenic pollutants in an environment medium is reduced, 20mg/kgAs (III) solution and 20mg/kgAs (V) solution are mixed in equal volume, the pH is regulated to 3.0-5.0, the zirconia-doped magnetic high-surface-activity biochar composite material is added in a solid-to-liquid ratio of 0.5g/L, after the zirconia-doped magnetic high-surface-activity biochar composite material is fully stirred for 6-12 h, the zirconia-doped magnetic high-surface-activity biochar composite material is magnetically separated from suspension by an external magnetic field (such as a magnet), and then the zirconia-doped magnetic high-surface-activity biochar composite material and a desorption solution (a mixed solution with the concentration of 0-1 mol/L, which is prepared by the molar ratio of sodium carbonate to dipotassium phosphate) are mixed according to the solid-to the solid ratio of 1:10, and the regeneration efficiency of the material is shown in fig. 4.
As is clear from FIG. 4, the desorption efficiency of arsenic increases rapidly with the increase of the concentration of the desorption liquid, and the desorption efficiency of arsenic reaches a substantial equilibrium (arsenic desorption rate 95.83% -99.16%) in the range of 0.1-1 mol/L of the desorption mixture. Therefore, in order to reduce the regeneration cost of the zirconia doped high-surface-activity magnetic carbon composite material, the concentration of the desorption mixed solution is preferably 0.1-0.5 mol/L.
Thereafter, the regenerated zirconia doped magnetic high-surface-activity biochar composite material is further added with arsenic-containing solution according to the steps to adsorb and remove arsenic pollutants, and desorption treatment and material regeneration are sequentially carried out, and the result is shown in fig. 5.
As can be seen from FIG. 5, the adsorption and removal rate of arsenic by the initial zirconia doped magnetic high-surface-activity biochar composite material can reach 99.31% (the recycling cycle number of the material is 0), and then the adsorption and removal rate of arsenic by the composite material is gradually reduced along with the increase of the recycling cycle number of the recycled material, especially after the recycling for 6-8 times, the adsorption and removal rate of arsenic by the composite material is only 46.08-78.67%, but under the recycling condition for 1-5 times, the adsorption and removal rate of arsenic by the composite material can still be kept at 93.59-99.29%. The result shows that the obtained zirconia doped magnetic high-surface-activity biochar composite material can be regenerated and recycled for 4-5 times, and can realize high-efficiency adsorption removal of arsenic pollution in water.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention fall within the protection scope of the present invention.
Claims (5)
1. The application of the zirconia doped magnetic high-surface-activity biochar composite material in removing arsenic-containing pollutants is characterized in that the zirconia doped magnetic high-surface-activity biochar composite material is prepared by mixing and pyrolyzing organic matters and soluble ferric salt to introduce ferroferric oxide particles to obtain a magnetic biochar material, and directionally doping and loading zirconia fine particles on the magnetic biochar material, thereby preparing the zirconia doped magnetic high-surface-activity biochar composite material with a porous core-shell structure, and the method specifically comprises the following steps:
s101, mixing an organic matter with a soluble ferric salt solution, then sealing and placing for 12-24 hours, drying, continuously heating to 500-550 ℃ at a speed of 5-10 ℃/min under an inert atmosphere, pyrolyzing for 1-2 hours, and cooling to obtain a crude product of the magnetic biochar material;
the adding amount of iron ions in the soluble ferric salt solution is 8-10% of the total mass of the organic matters;
s102, adding a pore-forming agent into the crude magnetic biochar material, heating to 700-800 ℃ at a speed of 5-10 ℃/min under an inert atmosphere, pyrolyzing for 1-2 hours, sequentially cooling, washing, drying and grinding, and then separating from the obtained solid product under the action of an externally applied magnetic field to obtain the magnetic biochar material with high surface activity;
s103, after the high-surface-activity magnetic biochar material is dissolved, adding zirconium tetrachloride solution, stirring to form a homogeneous suspension, adding alkaline solution with the same volume as that of the zirconium tetrachloride solution, standing, and sequentially washing and drying the obtained solid to obtain the zirconia-doped high-surface-activity magnetic biochar composite material;
in S102, the pore-forming agent is one of sodium hydroxide, sodium bicarbonate and sodium carbonate;
in S103, the high-surface-activity magnetic biochar material is dissolved according to 1g: 50-100 mL of the solvent is mixed with the solvent, and the solvent is absolute ethyl alcohol and deionized water according to the volume ratio of 1-2: 1, mixing the obtained solution;
the alkaline solution is concentrated ammonia water or sodium hydroxide solution with the concentration of 0.25-0.3 mol/L.
2. The use according to claim 1, wherein,
in S101, the soluble ferric salt solution is a ferric salt solution or a ferrous salt solution or a mixed solution of ferric salt and ferrous salt in a molar ratio of 2:1;
the ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the ferrous salt is one or more of ferrous chloride, ferrous nitrate and ferrous sulfate.
3. The use according to claim 1, wherein in S103, the concentration of the zirconium tetrachloride solution is 0.05-0.1 mol/L, and the addition amount of the zirconium tetrachloride solution is 20-40 ml.
4. The use according to claim 1, wherein the method for regenerating the zirconia doped magnetic high surface activity biochar composite comprises the steps of:
mixing the zirconia doped magnetic high-surface-activity biochar composite material adsorbed with arsenic pollutants with a desorption solution, and stirring for 4-6 hours;
the desorption solution is a mixed solution prepared from sodium carbonate and dipotassium hydrogen phosphate according to a molar ratio of 1:1, and the concentration of the sodium carbonate and the dipotassium hydrogen phosphate in the mixed solution is 0.1-0.5 mol/L.
5. The use according to claim 4, wherein the zirconia doped magnetic high-surface-activity biochar composite material regenerated by the method is recycled for 4-5 times.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013126477A1 (en) * | 2012-02-22 | 2013-08-29 | University Of Florida Research Foundation, Inc. | Biochar/metal composites, methods of making biochar/metal composites, and methods of removing contaminants from water |
| CN104353440A (en) * | 2014-11-28 | 2015-02-18 | 南京信息工程大学 | Biomass resin based inorganic nano-oxide composite adsorbent and preparation method and application thereof |
| CN106732350A (en) * | 2016-11-18 | 2017-05-31 | 浙江大学 | The preparation method of the magnetic bio charcoal sorbing material repaired to arsenic cadmium combined pollution |
| CN110813239A (en) * | 2019-12-04 | 2020-02-21 | 绍兴文理学院 | Preparation method of biochar-loaded lanthanum-doped iron oxide |
| CN111547790A (en) * | 2020-06-22 | 2020-08-18 | 河南师范大学 | Preparation method of biomass water treatment environment functional material |
| CN111672466A (en) * | 2020-06-07 | 2020-09-18 | 桂林理工大学 | Preparation method and application of magnetic iron oxide/mulberry tree stalk biochar composite material |
| CN111672465A (en) * | 2020-06-07 | 2020-09-18 | 桂林理工大学 | Preparation method and application of ferroferric oxide-manganese dioxide/mulberry stem biochar composite material |
| CN111804276A (en) * | 2020-07-14 | 2020-10-23 | 安徽汇泽通环境技术有限公司 | Preparation method and application of zirconium hydroxide modified magnetic biochar adsorbing material |
| CN111925806A (en) * | 2020-07-20 | 2020-11-13 | 华东理工大学 | Sulfur-doped nano ferroferric oxide/biochar composite material as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180016162A1 (en) * | 2016-07-15 | 2018-01-18 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Magnetic Metal Oxide Biochar Composite Particles, and Their Use in Recovering Pollutants From Aqueous Solution |
-
2020
- 2020-12-16 CN CN202011498853.4A patent/CN112774625B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013126477A1 (en) * | 2012-02-22 | 2013-08-29 | University Of Florida Research Foundation, Inc. | Biochar/metal composites, methods of making biochar/metal composites, and methods of removing contaminants from water |
| CN104353440A (en) * | 2014-11-28 | 2015-02-18 | 南京信息工程大学 | Biomass resin based inorganic nano-oxide composite adsorbent and preparation method and application thereof |
| CN106732350A (en) * | 2016-11-18 | 2017-05-31 | 浙江大学 | The preparation method of the magnetic bio charcoal sorbing material repaired to arsenic cadmium combined pollution |
| CN110813239A (en) * | 2019-12-04 | 2020-02-21 | 绍兴文理学院 | Preparation method of biochar-loaded lanthanum-doped iron oxide |
| CN111672466A (en) * | 2020-06-07 | 2020-09-18 | 桂林理工大学 | Preparation method and application of magnetic iron oxide/mulberry tree stalk biochar composite material |
| CN111672465A (en) * | 2020-06-07 | 2020-09-18 | 桂林理工大学 | Preparation method and application of ferroferric oxide-manganese dioxide/mulberry stem biochar composite material |
| CN111547790A (en) * | 2020-06-22 | 2020-08-18 | 河南师范大学 | Preparation method of biomass water treatment environment functional material |
| CN111804276A (en) * | 2020-07-14 | 2020-10-23 | 安徽汇泽通环境技术有限公司 | Preparation method and application of zirconium hydroxide modified magnetic biochar adsorbing material |
| CN111925806A (en) * | 2020-07-20 | 2020-11-13 | 华东理工大学 | Sulfur-doped nano ferroferric oxide/biochar composite material as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Organic–inorganic interpenetrated hybrids based on cationic polymer and hydrous zirconium oxide for arsenate and arsenite removal;Jehu Perez et al.;《Chemical Engineering Journal》;20151202;第287卷;744-754 * |
| Removal of arsenate from contaminated waters by novel zirconium and zirconium-iron modified biochar;Md. Aminur Rahman et al.;《Journal of Hazardous Materials》;20201106;第409卷;No.124488 * |
| 改性吸附材料处理水体中砷的研究进展;许江城等;《水处理技术》;20200930;第46卷(第10期);6-11 * |
| 磁性核壳型砷吸附剂的制备及其除砷性能研究;张游;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20190215(第2期);9-44 * |
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