CN113181885A - Preparation and application of manganese carbide crosslinked sodium alginate modified biochar loaded nZVI - Google Patents

Preparation and application of manganese carbide crosslinked sodium alginate modified biochar loaded nZVI Download PDF

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CN113181885A
CN113181885A CN202110657438.7A CN202110657438A CN113181885A CN 113181885 A CN113181885 A CN 113181885A CN 202110657438 A CN202110657438 A CN 202110657438A CN 113181885 A CN113181885 A CN 113181885A
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manganese
sodium alginate
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iron
biochar
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CN113181885B (en
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管运涛
毛伟
张莹
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Shenzhen International Graduate School of Tsinghua University
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • 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
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    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • 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
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a preparation method and application of manganese carbide cross-linked sodium alginate modified charcoal-loaded nano zero-valent iron, wherein the preparation method comprises the following steps: s1, mixing and fully stirring a manganese (II) salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying; s2, sintering and carbonizing the solid particles at the temperature of 900 ℃ of 300-; s3, fully stirring the iron (II) salt solution and the manganese carbide cross-linked sodium alginate modified biochar under the protection of inert gas, and dropwise adding NaBH4Stirring the solution for 30min-1h, washing, centrifuging, freeze drying, and grinding in an inert gas box to obtain carbonized productThe manganese crosslinked sodium alginate modified charcoal loads nano zero-valent iron. The composite material prepared by the invention can be applied to the synergistic adsorption of As (III), Cd (II) and phosphorus retention, and has wide application prospect in the environment.

Description

Preparation and application of manganese carbide crosslinked sodium alginate modified biochar loaded nZVI
Technical Field
The invention relates to the field of environmental management, in particular to a preparation method of manganese carbide crosslinked sodium alginate modified charcoal-loaded nano zero-valent iron (nZVI) and application thereof in the fields of heavy metal adsorption and phosphorus retention.
Background
With the increasing frequency of human activities, a large amount of organic matters, heavy metals, nutrient elements and the like enter the environment along with sewage and automobile exhaust, the ecological damage is gradually increased, and the human health is potentially harmed, for example, the national soil general survey finds that the standard exceeding rate of Cd (II) in soil reaches 7%. Meanwhile, heavy metal pollution in the environment is generally mainly caused by co-pollution of anions and cations, for example, metal anions such as Cr (VI), As (III), As (V) and the like coexist with metal cations such as Cd (II), Cu (II), Ni (II), Zi (II) and the like in the environment. Most researchers at present are dedicated to the carbonization of solid wastes (such as agricultural wastes and forestry wastes) to prepare biochar to remove heavy metal ions, so as to realize resource utilization of the solid wastes and adsorption of heavy metals, however, the biochar is negatively charged due to abundant organic functional groups on the surface, so that the biochar has a relatively good adsorption effect on heavy metal cations, but the adsorption effect on heavy metal anions is almost zero. Therefore, at present, material research and development mainly focuses on research on the adsorption performance of single heavy metal anions or heavy metal cations, and few reports are reported on a preparation method of a high-efficiency material for realizing heavy metal anion and cation synergistic adsorption and soil phosphorus retention.
Disclosure of Invention
The invention mainly aims to provide a preparation method of manganese carbide crosslinked sodium alginate modified charcoal-loaded nano zero-valent iron and application of the method in heavy metal cation and anion adsorption and phosphorus retention.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of manganese carbide cross-linked sodium alginate modified charcoal-loaded nano zero-valent iron comprises the following steps:
s1, mixing and fully stirring a manganese (II) salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying;
s2, sintering and carbonizing the dried solid particles in the step S1 at the temperature of 900 ℃ of 300-;
s3, fully stirring the iron (II) salt solution and the manganese carbide cross-linked sodium alginate modified biochar obtained in the step S2 under the protection of inert gas, and dropwise adding NaBH4And fully stirring the solution for 30min-1h, washing, centrifuging, freeze-drying, and grinding and collecting in an inert gas box to obtain the manganese carbide crosslinked sodium alginate modified charcoal loaded nano zero-valent iron.
Preferably, the manganese (II) salt solution in step S1 is manganese sulfate; in the manganese (II) salt solution, the mass concentration of the manganese (II) salt is 4.1%; the mass ratio of the manganese (II) salt in the manganese (II) salt solution to the biochar precursor is 1.69: 1.
Preferably, the iron (II) salt solution in step S3 is an iron sulfate solution prepared from FeSO4·7H2O is completely dissolved in the degassed water to obtain the product; in the iron (II) salt solution, the mass concentration of the iron (II) salt is 7%; the mass of the iron (II) salt in the iron (II) salt solution, the mass of the manganese carbide crosslinked sodium alginate modified biochar obtained in the step S2 and the NaBH4NaBH in solution4The mass ratio of (A) to (B) is 7.44:1.5: 1.512; the NaBH4NaBH in solution4The mass concentration of (2) is 3%; the washing, centrifuging, freeze-drying and grinding collection in the inert gas box in the step S3 mean that: mixing ethanol and degassed water 1: washing 1, centrifuging at 9000rpm for 3min, repeating for three times, drying at-48 deg.C for 12 hr with freeze dryer, and grinding in nitrogen box.
Preferably, the biochar precursor is prepared from garden solid waste, preferably is prepared from euphorbia hirta, and more preferably is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
Preferably, in the step S1, after the manganese (II) salt solution and the biochar precursor are mixed and sufficiently stirred, the mixture is treated for 30min under ultrasonic, and then a 2 wt% sodium alginate solution is added dropwise.
Preferably, said sieving in said step S2 means sieving with a 60-mesh sieve.
Preferably, the dropping in the step S1 refers to dropping by using a peristaltic pump with the rotating speed of 3 mL/min; the dripping of the step S3 is performed by adopting a peristaltic pump with the rotating speed of 2 mL/min.
A composite material prepared by the preparation method.
The application of the composite material in treating heavy metal ions and/or phosphorus is provided.
Preferably, the heavy metal ions are at least one of as (iii) ions, cd (ii) ions.
Preferably, the application refers to the synergistic and efficient adsorption of As (III) anions and Cd (II) cations and the retention of phosphorus in soil by the composite material.
The beneficial effects of the invention include: the preparation method is characterized in that manganese crosslinked sodium alginate is loaded on the surface of a charcoal precursor, the charcoal precursor is sintered and carbonized at high temperature to obtain manganese carbide crosslinked sodium alginate modified charcoal (the charcoal precursor is converted into charcoal after being sintered at high temperature), and nanometer zero-valent iron is loaded on the manganese carbide crosslinked sodium alginate modified charcoal to obtain a final composite material.
Drawings
FIG. 1 is an XRD pattern of composites prepared in examples 1-3 of the present invention.
FIG. 2 is a FT-IR plot of composites prepared in examples 1-2 of the present invention.
FIG. 3 is an SEM image of composite materials prepared in examples 1-3 of the present invention.
FIG. 4 is a kinetic curve of As (III) adsorption of the composite materials prepared in examples 1-3 of the present invention.
FIG. 5 is a kinetic curve of Cd (II) adsorption of the composite materials prepared in examples 1-3 of the present invention.
FIG. 6 is a kinetic curve of phosphorus adsorption of the composite material prepared in example 2 of the present invention.
FIG. 7 is a kinetic curve of the composite material prepared in example 2 of the present invention adsorbing single and mixed As (III) and Cd (II).
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The embodiment of the invention provides a preparation method of manganese carbide crosslinked sodium alginate modified charcoal loaded nano zero-valent iron, which comprises the following steps: s1, mixing and fully stirring a manganese (II) salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying; s2, sintering and carbonizing the dried solid particles in the step S1 at the temperature of 900 ℃ of 300-; s3, fully stirring the iron (II) salt solution and the manganese carbide cross-linked sodium alginate modified biochar obtained in the step S2 under the protection of inert gas, and dropwise adding NaBH4And fully stirring the solution for 30min-1h, washing, centrifuging, freeze-drying, and grinding and collecting in an inert gas box to obtain the manganese carbide crosslinked sodium alginate modified charcoal loaded nano zero-valent iron.
According to the technical scheme, the biochar is modified by selecting a manganese element cross-linked sodium alginate and nano zero-valent iron loading mode, so that the adsorption effect of the composite material on heavy metal anions and phosphorus is improved, the synergistic fixation of the composite material on the heavy metal anions and the phosphorus is realized, and the practical application capacity of the composite material is improved.
In a preferred embodiment, the manganese (II) salt solution in step S1 is manganese sulfate; in the manganese (II) salt solution, the mass concentration of the manganese (II) salt is 4.1%; the mass ratio of the manganese (II) salt in the manganese (II) salt solution to the biochar precursor is 1.69: 1.
In a preferred embodiment, the sintering carbonization of step S2 is performed under the protection of inert gas.
In a preferred embodiment, the sinter carbonization is a sinter carbonization at 600 ℃ for 2 h.
In a preferred embodiment, the iron (II) salt solution in step S3 is an iron sulfate solution prepared from FeSO4·7H2O is completely dissolved in the degassed water to obtain the product; in the iron (II) salt solution, the mass concentration of the iron (II) salt is 7%; the mass of the iron (II) salt in the iron (II) salt solution, the mass of the manganese carbide crosslinked sodium alginate modified biochar obtained in the step S2 and the NaBH4NaBH in solution4The mass ratio of (A) to (B) is 7.44:1.5: 1.512; the NaBH4NaBH in solution4The mass concentration of (2) is 3%; the washing, centrifuging, freeze-drying and grinding collection in the inert gas box in the step S3 mean that: mixing ethanol and degassed water 1: washing 1, centrifuging at 9000rpm for 3min, repeating for three times, drying at-48 deg.C for 12 hr with freeze dryer, and grinding in nitrogen box.
In a preferred embodiment, the biochar precursor is prepared from garden solid waste, preferably the biochar precursor is prepared from euphorbia hirta, and more preferably the biochar precursor is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
In a preferred embodiment, after the manganese (II) salt solution and the biochar precursor are mixed and sufficiently stirred in step S1, the mixture is treated for 30min under ultrasound, and then a 2 wt% sodium alginate solution is added dropwise.
In a preferred embodiment, said sieving in said step S2 is 60 mesh sieving.
In a preferred embodiment, the sieving in the preparation of the biochar precursor is 60 mesh sieving.
In a preferred embodiment, the dropping of step S1 is performed by using a peristaltic pump with a rotation speed of 3 mL/min; the dripping of the step S3 is performed by adopting a peristaltic pump with the rotating speed of 2 mL/min.
The embodiment of the invention also provides a composite material prepared by the preparation method.
The embodiment of the invention also provides application of the composite material in treatment of heavy metal ions and/or phosphorus.
In a preferred embodiment, the heavy metal ions are at least one of as (iii) anions, cd (ii) cations.
In a preferred embodiment, said application means that said composite material synergistically adsorbs as (iii) anions and cd (ii) cations.
The present invention is further illustrated by the following specific examples.
Example 1
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from greenish to dark green, putting 30g of the dried large-leaf oilseed rape in a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water, and repeating the steps for a plurality of times until the cleaning solution is free of soil. Drying cleaned herba Euphorbiae Lathyridis in oven at 60 deg.C for 24h, pulverizing with small pulverizer, sieving with 60 mesh sieve, and storing in drying oven.
16.9g MnSO4Dissolving the materials in 400mL of distilled water completely, adding 10g of crushed large-leaf clover, stirring fully and performing ultrasonic treatment for 30min, dropwise adding a 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min), forming fine granular substances on the surface of the large-leaf clover through a crosslinking reaction, and quickly forming micro-spherical particles. And washing the prepared microspherical particles with deionized water for three times, recovering solid particles, drying in an oven at 80 ℃ for 24 hours, and removing water.
Reacting the dried solid particles in a muffle furnace at 600 ℃ for 2h, naturally cooling, washing with deionized water to remove metal elements, drying in an oven at 80 ℃ for 24h, grinding microspherical composite carbonized particles by using an agate mortar, ball-milling for 15min at a rotating speed of 220rpm by using a ball mill to recover powder, grinding the powder by using the agate mortar again and sieving by using a 60-mesh sieve to obtain the carbonized Mn crosslinked sodium alginate modified biochar, which is expressed as Mn/BC-SA.
Example 2
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape in a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water, and repeating the steps for a plurality of times until the cleaning solution is free of soil. Drying cleaned Euphorbiae Lathyridis semen in oven at 60 deg.C for 24 hr, pulverizing with small pulverizer, sieving with 60 mesh sieve, and storing in drying oven;
16.9g MnSO4dissolving the materials in 400mL of distilled water completely, adding 10g of crushed large-leaf clover, stirring fully and performing ultrasonic treatment for 30min, dropwise adding a 2 wt% sodium alginate solution (a fine granular substance is formed on the surface of the large-leaf clover through a cross-linking reaction) through a peristaltic pump (the rotating speed is 3mL/min), and quickly forming micro-spherical particles. And washing the prepared microspherical particles with deionized water for three times, recovering solid particles, drying in an oven at 80 ℃ for 24 hours, and removing water.
Reacting the dried solid particles in a muffle furnace at 600 ℃ for 2h, naturally cooling, washing with deionized water to remove metal elements, drying in an oven at 80 ℃ for 24h, grinding microspherical composite carbonized particles by using an agate mortar, ball-milling for 15min at a rotating speed of 220rpm by using a ball mill to recover powder, grinding the powder by using the agate mortar again and sieving by using a 60-mesh sieve to obtain the carbonized Mn crosslinked sodium alginate modified biochar, which is expressed as Mn/BC-SA.
7.44g FeSO4·7H2Dissolving O in 100mL of degassed water completely, adding 1.5g of the prepared carbonized Mn crosslinked sodium alginate modified biochar, stirring for 2h under the protection of nitrogen, and dropwise adding 50mL of sodium borohydride (containing 1.512g of NaBH) through a peristaltic pump (the rotating speed is 2 mL/min)4The solution was then stirred well for 1h, mixed with ethanol and degassed water 1: washing the raw materials, centrifuging the raw materials at 9000rpm of a centrifugal machine for 3min, repeating the steps for three times, drying the raw materials for 12h at-48 ℃ by using a freeze dryer, grinding and collecting the raw materials in a nitrogen box to obtain the carbonized Mn crosslinked sodium alginate modified biochar loaded nano zero-valent iron (the nano zero-valent iron is loaded on the carbonized Mn crosslinked sodium alginate modified biochar), expressed as Mn/BC-SA @ nZVI, and storing the obtained product in a refrigerator at-5 ℃.
Example 3
7.44g FeSO4·7H2O is completely dissolved in 100mL of degassed water, and 50mL of a solution containing 1.512g of NaBH are added dropwise via a peristaltic pump (2 mL/min)4The solution was then stirred well for 1h, mixed with ethanol and degassed water 1: washing with water 1, centrifuging at 9000rpm for 3min, repeating for three times, drying at-48 deg.C for 12 hr with freeze dryer, grinding in nitrogen box, collecting to obtain nanometer zero-valent iron (nZVI), and storing in-5 deg.C refrigerator.
XRD characterization was performed on the composites prepared in examples 1-3, as shown in FIG. 1. From an XRD (X-ray diffraction) spectrum, the nano zero-valent iron is loaded on the carbonized Mn cross-linked sodium alginate modified biochar, so that the crystallinity of the composite material can be obviously improved, and the generation of the nano zero-valent iron and MnO in the material can be detected.
FT-IR characterization was performed on the composites prepared in examples 1 and 2, as shown in figure 2. From the FT-IR spectrum, it can be found that the spectrum is 2000cm from 400--1The absorption peak wavelengths were Mn-O, -COONa, Mn-OH, and C ═ O stretching vibration, whereby it was sufficiently confirmed that MnO was generated by carbonization.
SEM characterization of the composite materials prepared in examples 1-3, as shown in FIG. 3, it can be found that when the carbonized Mn crosslinked sodium alginate is attached to the surface of the biochar, the large specific surface area of the biochar provides attachment sites for the Mn crosslinked sodium alginate microspheres. The adsorption performance of the composite material can be improved by loading the nano zero-valent iron, and the graph (e) in fig. 3 shows that the square granular nano zero-valent iron is successfully loaded on the surface of the composite material.
FIG. 4 is a kinetic curve diagram of the adsorption of heavy metals As (III) by the composite materials prepared in examples 1-3, wherein the reaction conditions are as follows: 30mL of a solution containing 15mg of the composite material and 10mg/L of As (III). Compared with the examples 1 and 3, the Mn carbide cross-linked sodium alginate modified biochar loaded nano zero-valent iron composite material can efficiently and rapidly adsorb As (III), and the adsorption kinetics curve shows that the concentration of As (III) can be completely adsorbed within 50min, so that the adsorption performance of As (III) is obviously improved by loading the nano zero-valent iron modified composite material.
FIG. 5 is a kinetic curve diagram of the composite materials prepared in examples 1-3 for adsorbing heavy metal Cd (II), wherein the reaction conditions are as follows: 30mL of a solution containing 15mg of the composite and 10mg/L of Cd (II). Compared with the embodiment 1 and the embodiment 3, the Mn carbide crosslinked sodium alginate modified biochar loaded nano zero-valent iron composite material can more efficiently and quickly adsorb Cd (II), so that the adsorption performance of the loaded nano zero-valent iron modified composite material on Cd (II) is obviously improved.
FIG. 6 is a kinetic graph of phosphorus fixation for the composite material prepared in example 2, under the following reaction conditions: 30mL of a composition containing 15mg of the composite and 10mg/L P (KH)2PO4) The solution of (1). The carbonized Mn crosslinked sodium alginate modified charcoal-loaded nano zero-valent iron composite material can efficiently and quickly fix phosphorus, so that the composite material can rapidly and efficiently fix the phosphorus, prevent water eutrophication, retain the phosphorus in soil and prevent loss of phosphorus fertilizer in the soil.
FIG. 7 is a graph showing the cooperative adsorption kinetics of As (III) and Cd (II) by the composite material prepared in example 2, wherein the reaction conditions are as follows: (1) single cd (ii) solution: 30mL of a solution containing 15mg of the composite material and 20mg/L of Cd (II); (2) single as (iii) solution: 30mL of a solution containing 15mg of the composite material and 20mg/L of As (III); (3) mixing the solution: 30mL of a solution containing 15mg of the composite material, 20mg/L of As (III) and 20mg/L of Cd (II); in fig. 7, the curve of the mixed solution cd (ii) represents the adsorption kinetics curve of the composite material for cd (ii) in the mixed solution, and the curve of the mixed solution as (iii) represents the adsorption kinetics curve of the composite material for as (iii) in the mixed solution. The method shows that under the condition of the same composite material concentration, compared with the method for adsorbing single As (III) and Cd (II), the mixed heavy metal solution can be more quickly and efficiently adsorbed by the composite material, and the composite material can synergistically and efficiently remove metal anions and cations, particularly synergistically adsorb As (III) anions and Cd (II) cations, so that the composite material has a wide application prospect in environmental management.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.

Claims (10)

1. A preparation method of manganese carbide cross-linked sodium alginate modified biochar loaded nano zero-valent iron is characterized by comprising the following steps:
s1, mixing and fully stirring a manganese (II) salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying;
s2, sintering and carbonizing the dried solid particles in the step S1 at the temperature of 900 ℃ of 300-;
s3, fully stirring the iron (II) salt solution and the manganese carbide cross-linked sodium alginate modified biochar obtained in the step S2 under the protection of inert gas, and dropwise adding NaBH4And fully stirring the solution for 30min-1h, washing, centrifuging, freeze-drying, and grinding and collecting in an inert gas box to obtain the manganese carbide crosslinked sodium alginate modified charcoal loaded nano zero-valent iron.
2. The method of claim 1, wherein: the manganese (II) salt solution in step S1 is manganese sulfate; in the manganese (II) salt solution, the mass concentration of the manganese (II) salt is 4.1%; the mass ratio of the manganese (II) salt in the manganese (II) salt solution to the biochar precursor is 1.69: 1.
3. The method of claim 1, wherein: the iron (II) salt solution in the step S3 is ferrous sulfate solution prepared from FeSO4·7H2O is completely dissolved in the degassed water to obtain the product; in the iron (II) salt solution, the mass concentration of the iron (II) salt is 7%; the mass of the iron (II) salt in the iron (II) salt solution, the mass of the manganese carbide crosslinked sodium alginate modified biochar obtained in the step S2 and the NaBH4NaBH in solution4Is 7.44:1.5: 1.512; the NaBH4NaBH in solution4The mass concentration of (2) is 3%;
the washing, centrifuging, freeze-drying and grinding collection in the inert gas box in the step S3 mean that: mixing ethanol and degassed water 1: washing 1, centrifuging at 9000rpm for 3min, repeating for three times, drying at-48 deg.C for 12 hr with freeze dryer, and grinding in nitrogen box.
4. The method of claim 1, wherein: the biochar precursor is prepared from garden solid waste, preferably is prepared from euphorbia hirta, and more preferably is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
5. The method of claim 1, wherein: in the step S1, the manganese (II) salt solution and the biochar precursor are mixed and fully stirred, then the mixture is treated for 30min under ultrasonic, and then 2 wt% of sodium alginate solution is dripped.
6. The method of claim 1, wherein: the screening in the step S2 means screening by a 60-mesh screen.
7. The method of claim 1, wherein: the step S1 of dripping is to adopt a peristaltic pump with the rotating speed of 3mL/min to drip; the dripping of the step S3 is performed by adopting a peristaltic pump with the rotating speed of 2 mL/min.
8. A composite material produced by the production method according to any one of claims 1 to 7.
9. Use of the composite material of claim 8 for the treatment of heavy metal ions and/or phosphorus.
10. The use of claim 9, wherein: the heavy metal ions are at least one of As (III) anions and Cd (II) cations, and preferably, the application refers to that the composite material synergistically and efficiently adsorbs the As (III) anions and the Cd (II) cations and retains phosphorus in soil.
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