CN114247426B - Biochar-loaded natural iron-containing mineral magnetic adsorbent and preparation method and application thereof - Google Patents
Biochar-loaded natural iron-containing mineral magnetic adsorbent and preparation method and application thereof Download PDFInfo
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- CN114247426B CN114247426B CN202111507713.3A CN202111507713A CN114247426B CN 114247426 B CN114247426 B CN 114247426B CN 202111507713 A CN202111507713 A CN 202111507713A CN 114247426 B CN114247426 B CN 114247426B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 144
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- 239000011707 mineral Substances 0.000 title claims abstract description 74
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 72
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052745 lead Inorganic materials 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
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- 239000011148 porous material Substances 0.000 description 4
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid 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 physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention provides a biochar-loaded natural iron-containing mineral magnetic adsorbent, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Washing, drying, crushing and sieving biomass raw materials, drying and sieving natural iron-containing minerals; 2) Mixing biomass raw materials and natural iron-containing minerals in deionized water, mechanically stirring, carrying out vacuum drying, carrying out pyrolysis in an atmosphere tube furnace under the protection of nitrogen, cooling to room temperature, and sieving to obtain a biochar-loaded magnetite material; 3) And (3) placing the biochar-loaded natural iron-containing mineral material into an alkalizing agent for ultrasonic vibration impregnation, filtering, vacuum drying, carrying out pyrolysis in an atmosphere tube furnace under the protection of nitrogen, cooling to room temperature, and sieving to obtain the biochar-loaded natural iron-containing mineral magnetic adsorbent. The biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the invention has strong magnetism, extremely strong adsorption performance on heavy metals in wastewater, easy recovery, high recovery rate, simple preparation process and no secondary pollution.
Description
Technical Field
The invention belongs to the field of water pollution treatment, relates to a material for heavy metal wastewater treatment, and a preparation method and application thereof, and in particular relates to a biochar-loaded natural iron-containing mineral magnetic adsorbent, and a preparation method and application thereof.
Background
The density of heavy metal, i.e. simple substance, is higher than 4.5 g.cm -3 Such as lead, zinc, copper, nickel, mercury, copper, chromium, etc. The heavy metals have strong migration, enrichment and nondegradability, and the long-term exposure to low-concentration heavy metal pollution can seriously harm the health and ecological safety of human bodies. Lead and lead compounds have strong toxicity to human bodies, lead poisoning can cause abdominal cramps, hepatitis, general neuritis, toxic encephalitis, lead dissolution and the like, zinc poisoning can cause acute gastroenteritis symptoms, and excessive zinc can also have corrosion effect on digestive tracts, so shock is easy to cause death. Lead-zinc pollution has become one of the main pollutants of heavy metal pollution in current water bodies.
At present, there are many conventional methods for treating wastewater polluted by heavy metals, such as chemical precipitation, ion exchange, electrolysis, membrane separation, etc., but they all have respective disadvantages such as other pollution, complex operation, high cost, etc., which have limited their applications. Therefore, research on an efficient, green and economic treatment mode for heavy metal pollution has become a current hot spot and a leading edge.
Biochar is a green, low-cost and carbon-rich porous material prepared by pyrolyzing waste biomass under the condition of limiting oxygen. The biochar has huge specific surface area, complex surface active functional groups and stable chemical properties, and can keep stable properties under strong acid, strong alkali and high pressure conditions, thereby playing an important role in the aspect of water environment pollution treatment. The biochar is used as a powdery adsorbent, is not easy to recycle and recycle in the practical engineering application process, and can be quickly separated and recycled by introducing a magnetic material to magnetize the biochar.
At present, many methods for preparing magnetic biochar exist, and most of the methods adopt a chemical reagent to load magnetic nano particles on the biochar by adopting a dipping method, a liquid phase precipitation/reduction method and the like, but the prepared material is generally weak in magnetism, and the operation steps are complex and uncontrollable. But only adopts minerals with stronger magnetism such as magnetite and the like to modify the biochar, which greatly improves the magnetism of the material and can cause the situation that the adsorption efficiency of the biochar is not obviously increased or even reduced. By adopting a filtering recovery method, if the pore diameter of the filter membrane is large, the filter is not clean, so that the activated carbon with saturated adsorption remains in the wastewater, and heavy metal pollution redissolution is generated; when the pore diameter of the filter membrane is too small, the filtering speed is very slow, the efficiency is low, and the pressurizing treatment increases the cost. Therefore, it is needed to develop a biochar magnetic material with strong adsorptivity and strong magnetism and easy recovery.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of the biochar loaded natural iron-containing mineral magnetic adsorbent, which has strong magnetism, high recovery rate, extremely strong adsorption performance on heavy metals in wastewater, simple treatment process, environment friendliness and no secondary pollution.
The invention further aims at providing a biochar-loaded natural iron-containing mineral magnetic adsorbent.
The invention also provides a treatment method of the heavy metal-containing wastewater.
In order to achieve the above purpose, the invention provides a preparation method of a biochar-loaded natural iron-containing mineral magnetic adsorbent, which comprises the following steps:
(1) Washing biomass raw materials with deionized water to be neutral, soaking for 10-14 hours, taking out, drying at 80-105 ℃ for 3-5 hours, crushing, sieving with a 100-mesh sieve, drying natural iron-containing minerals at 105-120 ℃ for 5-8 hours, and sieving with a 200-mesh sieve;
(2) Mixing 2-8 parts by mass of biomass raw materials and 0.3-2 parts by mass of natural iron-containing minerals in 50-200 parts by mass of deionized water, mechanically stirring for 3-6 hours, drying in a vacuum drying oven at 80-105 ℃ for 5-8 hours, then placing in an atmosphere tube furnace under the protection of nitrogen, heating to 450-550 ℃ for pyrolysis for 2-4 hours, cooling to room temperature, and sieving with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral material;
(3) And (3) placing the obtained biochar-loaded natural iron-containing mineral material into an alkalizing agent, carrying out ultrasonic vibration impregnation for 1-3 h, filtering, vacuum drying at 80-105 ℃ for 5-8h, heating to 300-500 ℃ in an atmosphere tube furnace under the protection of nitrogen, carrying out high-temperature pyrolysis for 2-4h, cooling to room temperature, and sieving with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral magnetic adsorbent.
As described above, preferably, the biomass feedstock comprises: one or more of straw, tea residue and wood dust, wherein the natural iron-containing mineral comprises one or two of magnetite and maghemite, and the alkalizing agent comprises KOH aqueous solution, naOH aqueous solution or Na 2 CO 3 An aqueous solution.
When two or three of straw, tea dregs and wood dust are mixed, they can be mixed in any proportion, and when magnetite and maghemite are mixed, they can also be mixed in any proportion.
The temperature rising rate of the atmosphere tube furnace in the step (2) and the step (3) is 5-10 ℃/min, and the nitrogen inlet flow is 0.25-0.5L/min; introducing N for 20-30min before the temperature rising stage before high temperature pyrolysis in the atmosphere tube furnace 2 。
As described above, in the steps (2) and (3), N is preferably introduced for 20 to 30 minutes before the temperature rising stage of the atmosphere tube furnace before the high temperature pyrolysis 2 。
As described above, in the step (2), the mechanical stirring rate is preferably 180 to 250r/min.
As described above, in the step (3), the concentration of the alkalizing agent is preferably 1 to 3mol/L.
As described above, preferably, in the step (3), the mass-to-volume ratio (g/mL) of the biochar-loaded natural iron-containing mineral material to the alkalizing agent is 1:20-40.
As described above, preferably, the ultrasonic oscillation frequency in the step (3) is 30-50 KHz.
The invention also provides the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the preparation method.
The invention also provides a treatment method of the heavy metal-containing wastewater, the biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the preparation method is added into the heavy metal-containing wastewater, the mechanical stirring is carried out for 24-48 h, and the biochar loaded natural iron-containing mineral magnetic adsorbent which has adsorbed heavy metals is recovered by using a magnet.
As described above, preferably, the addition amount of the biochar-loaded natural iron-containing mineral magnetic adsorbent to the heavy metal-containing wastewater is 1-3 g/L, and the stirring rate is 120-150 r/min.
The invention has lower requirement on biomass raw materials, and the effects of the straw, tea leaves and wood chips which adopt carbon-containing materials with similar structures are not greatly different; magnetite and maghemite are iron-oxidizing mineral materials with stronger magnetism, so that biochar can be well magnetized; KOH aqueous solution, naOH aqueous solution, na 2 CO 3 The three aqueous solutions have stronger alkalinity, and any one of the aqueous solutions can be selected as an alkalizing modifier of the biochar-loaded natural iron-containing mineral magnetic material.
The preparation method of the biochar loaded natural iron-containing mineral magnetic adsorbent provided by the invention uses biomass raw materials to obtain the biochar, utilizes natural iron-containing minerals to modify the biochar to obtain a high-magnetic biochar material, uses an alkalizing agent to carry out alkalizing impregnation treatment to improve the porosity and specific surface area of the material, and increases oxygen-containing functional groups on the surface of the carbon, thereby greatly improving the adsorption performance of the material.
The invention takes the biomass such as tea slag, straw and the like as raw materials, has wide sources and easy acquisition, takes natural iron-containing minerals to directly load, has simple preparation method, does not involve liquid phase precipitation/reduction, has stable structure and low cost.
The prepared biochar loaded natural iron-containing mineral magnetic adsorbent has strong magnetism and high recovery rate, and can effectively avoid secondary pollution after treatment.
The biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the invention has good dispersibility in solution, extremely high adsorption performance on various composite heavy metals and simple process for treating heavy metal wastewater.
The invention has the beneficial effects that:
the invention provides a biochar-loaded natural iron-containing mineral magnetic adsorbent and a preparation method thereof.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a biochar-supported natural iron-containing mineral magnetic adsorbent prepared by the invention.
Fig. 2A is a graph showing the effect of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the invention on removing heavy metal Pb in wastewater.
Fig. 2B is a graph showing the effect of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the invention on removing heavy metal Zn in wastewater.
FIG. 3 is a graph showing the effect of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the invention on removing lead, zinc, copper, cadmium and nickel composite heavy metals from lead-zinc smelting wastewater.
Fig. 4 is a graph showing the effect rule of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the invention on the pH value of lead-zinc smelting wastewater.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of biochar-supported Natural iron-containing mineral Material
Washing the tea leaves residues with deionized water to be neutral, soaking for 12 hours, drying at 80 ℃ to constant weight, crushing and screening, and sieving with a 100-mesh sieve. Magnetite was dried at 110 ℃ for 5h, crushed and sieved through a 200 mesh sieve. Taking 10g of sieved tea leaves, respectively adding 0%, 15%, 20% and 25% (mass ratio) magnetite, mixing in deionized water, mechanically stirring for 4h, drying in a vacuum drying oven for 8h, placing the obtained mixed material in a quartz boat, and placing in an atmosphere tube furnaceIn, the preparation conditions were set as the rate of temperature increase: 5 ℃/min, residence time: 2h, nitrogen inlet flow: 0.5L/min, pyrolysis temperature 500 ℃. To ensure the vacuum environment of the atmosphere furnace, N is introduced for 20min before heating 2 . And carrying out oxygen-limited pyrolysis under the operation conditions, cooling the obtained material to room temperature, and sieving the cooled material with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral material (respectively marked with the biochar as 0% FBC, 15% FBC, 20% FBC and 25% FBC).
Example 2 removal of heavy metals Pb and Zn from solution by biochar-loaded Natural iron-containing mineral Material
Preparing Pb 2+ Initial concentration of 100mg/L, zn 2+ The single and composite solutions with initial concentration of 100mg/L were accurately measured for 50mL of each of the above solutions, 2g/L of each of the biochar-supported magnetite materials prepared in example 1 of the present invention was added, the temperature was set at 25℃and the reaction pH was 5.5, the stirring speed was 150rpm, and after 48 hours of reaction, the removal efficiency of the four materials of 0% FBC, 15% FBC, 20% FBC, 25% FBC prepared in example 1 of the present invention for heavy metals in single and mixed systems was tested, and the results are shown in Table 1.
Since wastewater containing heavy metals is generally acidic and activated carbon is alkaline, the pH is adjusted to an acidic environment here in order to simulate the pH of acidic wastewater, and the pH of each solution is adjusted to be uniform in order to ensure uniformity of conditions, so that experimental results are comparable.
TABLE 1 removal effect of biochar-loaded magnetite Material on heavy metals Pb and Zn
As can be seen from table 1, the loading of magnetite increases the adsorption effect of the material on Pb, zn compared to unmodified biochar. As the magnetite adding proportion increases, the adsorption effect of Pb and Zn all show a trend of increasing and then decreasing, because the magnetite with a low proportion is loaded and has a certain adsorption effect, the aperture of biochar is blocked by the excessive content of the added magnetite, so that the adsorption effect is poor, and when the magnetite adding proportion is 20%, the adsorption effect of Pb and Zn is optimal in a single and mixed system, but in general, the adsorption efficiency of the loaded natural iron-containing mineral on the biochar is not remarkably improved.
Example 3 preparation of biochar-loaded Natural iron-containing mineral magnetic adsorbent
2g of the biochar-loaded 20% magnetite material prepared in the embodiment 1 of the invention is weighed by an electronic balance, is put into 50mL of 2mol/L KOH solution, is immersed for 1h through 40KHz ultrasonic vibration, is dried for 6h in a vacuum drying oven at 105 ℃ after being filtered, and is put into an atmosphere tube furnace after being put into a quartz boat, wherein the preparation conditions are respectively set as the heating rate: 5 ℃/min, residence time: 2h, nitrogen inlet flow: 0.5L/min, pyrolysis temperature 500 ℃. To ensure the vacuum environment of the atmosphere furnace, N is introduced for 20min before heating 2 . And (3) carrying out oxygen limiting pyrolysis under the operation condition, cooling the obtained material to room temperature, and sieving the cooled material with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral magnetic adsorbent.
Grinding the obtained biochar loaded natural iron-containing mineral magnetic adsorbent sample with an agate mortar, sieving with a 200-mesh sieve, drying, then taking a small amount of powder to adhere to conductive adhesive, and observing the whole shape and surface morphology of the sample with a field emission scanning electron microscope under the accelerating voltage of 5kV, wherein an SEM (scanning electron microscope) chart is shown in figure 1.
As can be seen from fig. 1, the prepared biochar loaded natural iron-containing mineral magnetic adsorbent has a rough surface and densely distributed a large amount of fine particles, and part of pore structures of the biochar are filled, which is caused by magnetite particles entering the surface of the biochar in the pyrolysis process, so that magnetite is successfully loaded on the biochar material.
Example 4 effect of biochar-loaded Natural iron-containing mineral magnetic adsorbent on removal of heavy metals Pb and Zn in solution
Preparing Pb 2+ Contaminated solution with initial concentration of 50, 100, 150, 200, 250, 300, 400, 500mg/L and Zn 2+ The initial concentration was 25, 50, 75, 100, 150, 200, 300, 500mg/L of contaminated solution. 50mL of each solution was accurately measured, and 2g/L of the charcoal prepared in example 3 of the present invention was added, respectivelyThe natural iron-containing mineral magnetic adsorbent is loaded, the temperature is set to 25 ℃, the initial pH is 5.5, the stirring speed is 130rpm, and the reaction is carried out for 48 hours. The biochar loaded natural iron-containing mineral magnetic adsorbent for adsorbing heavy metals is recovered by a magnet, then a 10mL syringe is used for sucking the solution in the bottle, the content of residual heavy metals in the solution is tested, isothermal adsorption curves containing Pb and Zn are respectively measured to respectively show the adsorption effect of Pb and Zn, and the results are shown in FIG. 2A and FIG. 2B, wherein the abscissa Ce is adsorption equilibrium concentration, and the ordinate Qe is equilibrium adsorption capacity.
As can be seen from FIG. 2A, at the initial Pb 2+ The concentration is 50-200 mg/L, and the adsorption quantity of the material is increased rapidly along with the increase of the initial Pb concentration; at the initial Pb 2+ When the concentration is 250-500 mg/L, the adsorption quantity of the material is slowly increased, and finally the adsorption balance is reached. As can be seen from FIG. 2B, the adsorption amount of Zn by the material shows a different trend from Pb, and is in the initial Zn 2+ When the concentration is 25-150 mg/L, the adsorption quantity is slowly increased, and when Zn 2+ When the concentration is increased to 200-500 mg/L, the adsorption quantity of Zn by the material is obviously improved. As can be seen from FIGS. 2A and 2B, the maximum adsorption capacities of Pb and Zn were 78.68mg/g and 37.99mg/g, respectively.
Experimental example 5 comparison of adsorption effect of biochar-supported Natural iron-containing mineral magnetic adsorbent and activated carbon on heavy metals
Preparing Pb 2+ Initial concentration of 270mg/L, zn 2+ The single and composite solutions with initial concentration of 150mg/L were measured respectively and accurately, 50mL of the above solutions were measured respectively, 2g/L of the biochar-supported natural iron-containing mineral magnetic adsorbent and activated carbon prepared in example 3 of the present invention were added respectively, the temperature was set at 25℃and the reaction pH was 5, the stirring speed was 150rpm, and after 24 hours of reaction, the removal efficiency of the two materials for heavy metals in the single and mixed systems was compared, and the results are shown in Table 2.
TABLE 2 comparison of adsorption effects of magnetic adsorbents and activated carbon on heavy metals
As can be seen from Table 2, the biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the invention has the advantages of no Pb in a single system 2+ 、Zn 2+ Pb in a Mixed System 2+ The removal effect of the catalyst is far better than that of active carbon, and the catalyst can be used as an adsorption material for treating actual wastewater. But due to Pb 2+ 、Zn 2+ The biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the invention is more prone to preferentially adsorb Pb 2+ Pb in solution 2+ Zn when not fully adsorbed yet 2+ The adsorption amount of (2) is smaller.
Experimental example 6 simulation of removal of lead, zinc, copper, cadmium and Nickel composite heavy metals from lead-Zinc smelting wastewater
Lead, zinc, copper, cadmium and nickel composite heavy metal pollution lead-zinc smelting wastewater is simulated for testing, and the heavy metal concentrations are Pb:50.113mg/L, zn:30.039mg/L, cu:5.121mg/L, cd:5.107mg/L, ni:5.034mg/L, pH was adjusted to 2.0 and 4.0. 50mL of the solution is accurately measured, 2g/L of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared in the embodiment 3 of the invention is added, the temperature is set to 25 ℃, and the stirring speed is 150rpm. After 48h of reaction, the biochar loaded with natural iron-containing mineral magnetic adsorbent adsorbed with heavy metals is recovered by a magnet, then the solution in the bottle is sucked by a 10mL syringe, and the content of the residual heavy metals in the solution is tested, and the result is shown in FIG. 3. As can be seen from fig. 3, the removal rate of heavy metals is significantly improved with increasing pH. When the initial pH value of the solution is 4, the removal rate of all heavy metals in the wastewater exceeds 94%, wherein the removal rate of Pb exceeds 99.99%, the removal rate of Zn is 98.35%, cu is 96.32%, cd is 95.78%, and Ni is 94.31%. When the initial pH value of the solution is 2, the removal efficiency of each heavy metal is reduced. The removal rate of Pb and Zn in the solution still exceeds 90 percent. In addition, in the system with the pH value of 2.0 and 4.0, the pH value of the experimental group can be greatly increased to about 7.0 at the end of the experiment, and as shown in fig. 4, the harmless treatment of the acidic heavy metal wastewater is realized. The method has higher removal rate of heavy metals in the acidic wastewater with different pH values, has strong practicability and is suitable for popularization.
Experimental example 7 recovery of biochar-loaded Natural iron-containing mineral magnetic adsorbent
The magnetic adsorbent prepared in this example 3 has a saturation magnetization of 31.337emu/g, which is advantageous for recovery of materials. Simulating lead, zinc, copper, cadmium and nickel composite heavy metal polluted lead-zinc smelting wastewater, wherein the heavy metal concentrations are Pb:50.113mg/L, zn:30.039mg/L, cu:5.121mg/L, cd:5.107mg/L, ni:5.034mg/L and the pH was adjusted to 4.0. 50mL of the solution is accurately measured, 2g/L of the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared in the embodiment 3 of the invention is added, the temperature is set to 25 ℃, the stirring speed is 150rpm, the mechanical stirring is carried out for 24 hours, then a magnet is used for recycling the material, the recycled material is washed clean by deionized water and is dried in a vacuum dryer at 105 ℃ for 8 hours. The dried biochar loaded natural iron-containing mineral magnetic adsorbent is weighed, the weight of the biochar loaded natural iron-containing mineral magnetic adsorbent is 1.991g/L, and the recovery rate of the material is up to more than 99.5%. The biochar loaded natural iron-containing mineral magnetic adsorbent prepared by the method has strong magnetism and extremely high recovery rate, and effectively avoids secondary pollution formed by heavy metal redissolution because the biochar cannot be recovered in time after treatment.
According to the embodiment, the biochar loaded natural iron-containing mineral magnetic adsorbent and the preparation method thereof provided by the invention have the advantages that the magnetic adsorbent prepared by the preparation method is strong in magnetism and high in recovery rate, has extremely strong adsorption performance on heavy metals in wastewater, and is simple in treatment process, environment-friendly and free from secondary pollution.
While the foregoing is directed to the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and substitutions of parts and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (9)
1. A preparation method of a biochar loaded natural iron-containing mineral magnetic adsorbent is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Washing biomass raw materials with deionized water to be neutral, soaking for 10-14 hours, taking out, drying at 80-105 ℃ for 3-5 hours, crushing, and sieving with a 100-mesh sieve; drying natural iron-containing minerals at 105-120 ℃ for 5-8h, and sieving with a 200-mesh sieve;
(2) Mixing 2-8 parts by mass of biomass raw materials and 0.3-2 parts by mass of natural iron-containing minerals in 50-200 parts by mass of deionized water, mechanically stirring for 3-6 hours, filtering, drying in a vacuum drying oven at 80-105 ℃ for 5-8 hours, placing in an atmosphere tube furnace under the protection of nitrogen, heating to 450-550 ℃ for pyrolysis for 2-4 hours, cooling to room temperature, and sieving with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral material;
(3) Placing the obtained biochar-loaded natural iron-containing mineral material into an alkalizing agent, carrying out ultrasonic vibration impregnation for 1-3 h, filtering, vacuum drying at 80-105 ℃ for 5-8h, heating to 300-500 ℃ in an atmosphere tube furnace under the protection of nitrogen, carrying out high-temperature pyrolysis for 2-4h, cooling to room temperature, and sieving with a 200-mesh sieve to obtain the biochar-loaded natural iron-containing mineral magnetic adsorbent;
wherein the biomass raw material is one or more of straw, tea leaves and wood chips; the natural iron-containing mineral is one or two of magnetite and maghemite, and the alkalizing agent is KOH aqueous solution, naOH aqueous solution or Na 2 CO 3 An aqueous solution.
2. The method of manufacturing according to claim 1, characterized in that: the temperature rising rate of the atmosphere tube furnace in the step (2) and the step (3) is 5-10 ℃/min, and the nitrogen inlet flow is 0.25-0.5L/min; introducing N for 20-30min before the temperature rising stage before high temperature pyrolysis in the atmosphere tube furnace 2 。
3. The method of manufacturing according to claim 1, characterized in that: in the step (2), the mechanical stirring speed is 180-250 r/min.
4. The method of manufacturing according to claim 1, characterized in that: in the step (3), the solution concentration of the alkalizing agent is 1-3 mol/L.
5. The method according to claim 1 or 4, wherein: in the step (3), the mass-volume ratio of the biochar-loaded natural iron-containing mineral material to the alkalizing agent is 1:20-40.
6. The method of manufacturing according to claim 1, characterized in that: in the step (3), the ultrasonic oscillation frequency is 30-50 KHz.
7. A biochar-supported natural iron-containing mineral magnetic adsorbent prepared by the preparation method according to any one of claims 1 to 6, wherein the biochar-supported natural iron-containing mineral magnetic adsorbent has an adsorption capacity for Pb of 1 to 90mg/g and an adsorption capacity for Zn of 1 to 50mg/g.
8. A method for treating wastewater containing heavy metals, characterized in that the biochar-loaded natural iron-containing mineral magnetic adsorbent prepared by the preparation method according to any one of claims 1 to 6 or the biochar-loaded natural iron-containing mineral magnetic adsorbent according to claim 7 is added into the wastewater containing heavy metals, and is mechanically stirred for 24 to 48 hours, and the biochar-loaded natural iron-containing mineral magnetic adsorbent which has adsorbed heavy metals is recovered by a magnet.
9. The method for treating wastewater containing heavy metals as claimed in claim 8, wherein the addition amount of the biochar loaded natural iron-containing mineral magnetic adsorbent to the wastewater containing heavy metals is 1-3 g/L, and the stirring rate is 120-150 r/min.
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