CN112023878A - Preparation method of magnetic porous tea residue biochar for removing tetracycline in water body - Google Patents

Preparation method of magnetic porous tea residue biochar for removing tetracycline in water body Download PDF

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CN112023878A
CN112023878A CN202010771962.2A CN202010771962A CN112023878A CN 112023878 A CN112023878 A CN 112023878A CN 202010771962 A CN202010771962 A CN 202010771962A CN 112023878 A CN112023878 A CN 112023878A
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magnetic porous
drying
tea
tetracycline
tea residue
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范世锁
李斌
梅杨璐
唐俊
谢正鑫
周娜
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Anhui Agricultural University AHAU
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Anhui Agricultural University AHAU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • 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
    • B01J20/28—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
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    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention discloses a preparation method of magnetic porous tea residue biochar for removing tetracycline in a water body, and belongs to the field of resource recycling of product processing wastes. The waste tea dregs are used as raw materials, ferric chloride and potassium bicarbonate are used as modifiers, the ferric chloride is used for introducing magnetic substances, and the potassium bicarbonate is used for manufacturing a pore structure. The main steps are as follows; firstly, carrying out hot water washing, drying and crushing on the tea leaves, and then carrying out hydrothermal treatment and drying on the tea leaves to obtain hydrothermal carbon; soaking and mixing the hydrothermal carbon, the ferric chloride and the potassium bicarbonate uniformly, and drying; in tubular horsePyrolyzing in a muffle furnace; acid washing, water washing, drying and ball milling are carried out on the modified tea residue carbon to obtain the magnetic porous tea residue biochar, and the specific surface area of the magnetic porous tea residue biochar is 965-1035 m2Per gram, the pore volume is 0.4219-0.5825 cm3(ii) in terms of/g. The initial concentration of the tetracycline is 10-100mg/L, and the removal rate of the magnetic porous tea residue biochar to the tetracycline in the water body exceeds 95%; the magnetic porous tea residue charcoal can provide a new approach for resource utilization of the waste tea residues.

Description

Preparation method of magnetic porous tea residue biochar for removing tetracycline in water body
Technical Field
The invention belongs to the technical field of resource recycling of product processing wastes, and particularly relates to magnetic porous tea residue biochar and a preparation method thereof.
Background
With the rapid development of tea consumption markets, the tea yield of China reaches more than 200 million tons every year. Tea leaves or tea products can generate a large amount of tea leaves after production or drinking, and how to perform resource utilization on tea leaf waste becomes a focus of attention in the tea industry and the ecological environment protection field.
Currently, biochar is of great interest as an adsorbent for pollutants in water. Biochar refers to a class of carbon-rich, highly aromatic solid substances produced by low temperature (<700 ℃) pyrolysis of biomass in a completely or partially anoxic state. Due to the characteristics of wide sources of preparation raw materials, large specific surface area, developed pores, rich functional groups and minerals and the like, the biochar has good application prospect in the field of water pollution control. The tea residue contains a large amount of cellulose, hemicellulose, lignin, protein, polysaccharide, mineral substances and other components, and is an ideal raw material for preparing the biochar.
At present, direct pyrolysis carbonization is a main method for preparing tea residue biochar, but the specific surface area of the original tea residue biochar obtained by direct pyrolysis carbonization is smaller than 100 m/g, the pore structure is not very developed, and the effect of directly serving as an adsorbent to remove pollutants in a water body is limited, so that the tea residue biochar can be modified to improve the adsorption effect. Before direct carbonization, the tea leaves can be subjected to hydrothermal treatment to be subjected to preliminary carbonization, so that the thermochemical reaction between the tea leaves and the modifier is facilitated. Commonly used modifiers include sulfuric acid, nitric acid, phosphoric acid, potassium hydroxide, sodium hydroxide, mineral (magnesium aluminum manganese iron), steam, and the like. However, the modifier has the problems of high reagent consumption, corrosivity, potential secondary pollution, generation of toxic and harmful tail gas and the like.
In addition, the separation and recovery of the adsorbent is also a key factor that is limited to practical applications. Most adsorbents are solid powders that are difficult to separate and recover after adsorbing contaminants in a body of water. It is considered that the magnetic component is supported by the adsorbent, and the solid-liquid separation of the adsorbent can be performed easily. The common method for loading magnetic components in the adsorbent is to precipitate Fe by chemical precipitation3O4Is introduced into the adsorbent. However, the chemical precipitation method adds the steps of adsorbent preparation, and the preparation process also always needs to be protected by nitrogen gas, so that an oxygen-free environment is ensured.
At present, the methods for removing tetracycline from water mainly include traditional microbial treatment, membrane treatment, photocatalytic oxidation, and the like, which all have certain limitations. The role of microorganisms is inhibited by antibiotics as in conventional microbial treatment, membrane treatment is limited by the efficiency of membrane plugging and removal, and photocatalytic degradation is limited by the choice of reactor size and photocatalyst. The adsorption method has the advantages of high efficiency, simple and convenient operation, simple process, no secondary pollution and the like, and is widely concerned and applied. The selection and preparation of the adsorbent are the key to the effectiveness of the adsorption process. The biomass adsorbent which has wide raw material sources, low cost, excellent adsorption effect and no secondary pollution is attracting much attention.
Disclosure of Invention
In order to realize the resource utilization of the waste tea residues, the invention provides a preparation method of magnetic porous tea residue biochar for removing tetracycline in a water body.
The preparation operation steps of the magnetic porous tea residue biochar for removing tetracycline in water are as follows:
(1) pretreatment of raw materials
Washing the tea leaves with hot water to remove impurities, caffeine and pigments in the tea leaves, washing the tea leaves until the tea leaves are colorless, drying the tea leaves, and crushing the tea leaves to obtain tea leaf powder;
(2) hydrothermal treatment
Mixing 3-5 g of tea leaves with 50-80 mL of pure water, reacting for 8-10 hours at 200 ℃ in a hydrothermal reaction kettle, carrying out solid-liquid separation, washing solids with an absolute ethyl alcohol solution for three times, and drying to obtain hydrothermal carbon;
(3) dipping treatment of modifier
Mixing hydrothermal carbon, ferric chloride and potassium bicarbonate according to a mass ratio of 10g:10g:60g, adding 200mL of pure water for immersion treatment, stirring for 2-4 h at the temperature of 15-35 ℃, and drying to obtain a mixed solid;
(4) charring and magnetizing treatment
Heating the mixed solid to 700 ℃ at a heating rate of 5 ℃/min in a tubular muffle furnace, carbonizing, keeping the temperature at 700 ℃ for 1-3 h, and cooling to room temperature to obtain a carbide;
(5) washing and drying
Washing the carbide in 100mL of 0.1 mol hydrochloric acid solution (HCl) with a concentration of 0.1 mol, performing suction filtration, washing and suction filtration for three times, washing with pure water until the pH value of an eluate is 6-8, drying the carbide, and performing ball milling treatment to obtain magnetic porous tea residue biochar;
the specific surface area of the magnetic porous tea residue biochar is 965-1035 m2Per gram, the pore volume is 0.4219-0.5825 cm3/g。
The technical scheme for further limiting is as follows:
in the step (1), the hot water is 80-100 ℃; the drying is carried out in a forced air drying oven at the temperature of 100-105 ℃; the crushing is carried out by crushing and sieving with a 40-mesh sieve.
In the step (2), the solid and the absolute ethyl alcohol are mixed and washed according to the volume ratio of 1: 20.
In the step (2), the step (3) and the step (5), the drying is drying in a forced air drying box.
And (5) performing ball milling, namely grinding for 2 minutes, and sieving by using a 100-mesh sieve.
The adsorption rate of the magnetic porous tea residue biochar to tetracycline in the water body reaches 98% when the initial concentration of the tetracycline in the water body is 10-50 mg/L; when the initial concentration of the tetracycline in the water body is 60-100mg/L, the removal rate is more than 95%.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the invention provides a preparation method of tea residue biochar with simple preparation process, which adopts waste tea residues as raw materials and potassium bicarbonate (KHCO)3) And ferric chloride (FeCl)3) As modifier, KHCO3The catalyst is a novel environment-friendly catalyst, has the advantages of good effect, no secondary pollution, low corrosivity and the like, and is an excellent pore-forming agent; FeCl3The magnetic material also has the characteristics of safety, harmlessness, low price and good effect, and is an excellent precursor for introducing the magnetic component. The preparation process has low cost and wide raw material source, promotes the resource utilization of the tea residue waste of tea factories or tea processing enterprises, and can reduce the waste of biomass resources and environmental pollution.
2. The invention can realize synchronous carbonization and magnetization to prepare the magnetic porous tea residue biochar. The prepared magnetic porous tea residue biochar has a developed pore structure, a large specific surface area and magnetic characteristics.
KHCO in the invention3The modification has the following functions: the specific surface area of the biochar is increased, and a developed pore structure is formed. The function of the ferric chloride is as follows: assisting KHCO3The specific surface area of the biochar is increased, a developed pore structure is manufactured, adsorption sites of more pollutants are introduced, and solid-liquid separation of the adsorbent is facilitated.
The mechanism for forming the developed pore structure involves the reaction formula (1) - (5): when the pyrolysis temperature exceeds 400 ℃, KHCO3Will decompose K2CO3And CO2、H2O gas (reaction formula (1)). When the pyrolysis temperature is 700 ℃, K2CO3Will decompose into K2O and CO2(reaction formula (2)), and, at the same time, K2CO3And K2O reacts with carbon in the tea leaves to form K and CO (equations (3) and (4)), and in addition, CO is produced2The gas can be reduced into CO gas by the carbon in the tea residue (reaction formula (5)). H formed during the reaction2O、CO2And CO gas will make mesopores and micropores. Further, K is embedded in tea leaf carbon2O and K also form mesopores and micropores.
2KHCO3 →K2CO3 + CO2 + H2O——（1）
K2CO3 → K2O + CO2———————（2）
K2CO3 +2C → 2K + 3CO——————（3）
K2O + C → 2K + CO————————（4）
CO2 + C → 2CO————————（5）
FeCl3The specific mechanism of generation of magnetic species during pyrolysis involves reactions (6) - (12): when the pyrolysis temperature is 200-330 ℃, FeCl3Can be thermally decomposed into FeOCl & H2O (reaction formula (6)), FeOCl. H2O further generates FeOOH (reaction formula (7)). When the pyrolysis temperature is 330 ℃ and 700 ℃, FeOOH is decomposed into Fe2O3(reaction formula (8)) Fe2O3Can react with carbon in tea leaves to generate Fe3O4(reaction formula (9)). Fe when the pyrolysis temperature exceeds 700 DEG C2O3、Fe3O4Fe (reaction formulas (10) - (12)) which is reduced by carbon components in the tea leaves;
200-330℃:
FeCl3+2H2O→FeOCl·H2O+2HCl(g) ————————（6）
FeOCl·H2O+2HCl(g) →FeOOH+3HCl(g) ————————（7）
330-700 ℃:
2FeOOH→Fe2O3+H2O————————（8）
6Fe2O3+C→4Fe3O4+CO2————————（9）
≥700℃:
2Fe2O3+3C→4Fe+3CO2————————（10）
Fe3O4+2C→3Fe+2CO2————————（11）
Fe3O4+4C→3Fe+4CO————————（12）
the specific surface area of the prepared magnetic porous tea residue biochar is as high as 965-1035 m2Per gram, the pore volume is 0.4219-0.5825 cm3/g。
3. The magnetic porous tea residue biochar can be used for removing pollutants in water, and achieves the purposes of resource utilization of waste tea residues and environmental protection. The magnetic porous tea residue biochar disclosed by the invention has a good effect of removing tetracycline in a water body. In a certain concentration range (0-100mg/L), the porous tea residue biochar with high specific area has good effect of removing tetracycline in water. When the initial concentration of the tetracycline is 10-100mg/L, the removal rate of the tea-residue porous tea-residue biochar on the tetracycline exceeds 95%, and the removal effect is obvious. Meanwhile, under the action of an external magnet, the magnetic porous tea residue biochar after tetracycline adsorption can be subjected to solid-liquid separation very easily, so that the effective recovery of the adsorbent is realized. The mechanism of the excellent tetracycline removing effect of the magnetic porous tea residue biochar relates to pore diffusion (the specific surface area and the pore structure of the biochar are determined), pi-pi stacking effect (the aromatic structure of the biochar is determined), and hydrogen bonding effect (the iron-containing and oxygen-containing functional groups of the biochar are determined).
Drawings
FIG. 1 is a scanning electron microscope image of 5 ten thousand times of the prepared magnetic porous tea residue biochar.
FIG. 2 is a Fourier infrared spectrum of the prepared magnetic porous tea residue biochar.
FIG. 3 shows the tetracycline removal rate of the magnetic porous tea residue charcoal in aqueous solutions with different initial concentration values according to the embodiment of the present invention.
FIG. 4 is a diagram showing a solid-liquid separation state after the magnetic porous tea residue biochar adsorbs tetracycline in a water body under the action of an additional magnet in the embodiment of the invention.
Detailed Description
The preferred embodiments of the present invention will be described in detail below. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
The specific preparation operation steps of the magnetic porous tea residue biochar for removing tetracycline in water are as follows:
(1) pretreatment of raw materials
Washing the waste tea leaves taken from a tea factory with water to remove impurities, putting the washed tea leaves into a forced air drying oven for drying at 105 ℃ for 24 hours, and drying in the forced air drying oven; pulverizing with a pulverizer, sieving with a 50 mesh sieve, and storing for use.
(2) Hydrothermal treatment
Mixing 5g of tea leaves and 80ml of pure water, adding the mixture into a hydrothermal reaction kettle, reacting for 10 hours at 200 ℃, and carrying out solid-liquid separation to obtain hydrothermal carbon; washing the hydrothermal carbon with absolute ethyl alcohol for three times; the ratio of the hydrothermal carbon to the absolute ethyl alcohol is 1: 20; and drying in a forced air drying oven at 105 ℃ for 10h to obtain the hydrothermal carbon.
(3) Dipping treatment of modifier
Heating water with charcoal: iron chloride: the potassium bicarbonate is prepared from the following raw materials in a mass ratio of 10g:10g:60g (1: 1: 6) of the raw materials are mixed, 200mL of pure water is added for immersion treatment, the mixture is stirred for 2 hours at the temperature of 25 ℃, and the mixture is put into an air-blast drying oven to be dried and removed of water, wherein the drying temperature is 105 ℃, and the drying time is 24 hours; obtaining the mixed solid of the hydrothermal carbon, the ferric chloride and the potassium bicarbonate.
(4) Charring and magnetizing treatment
And putting the mixed solid into a quartz boat, transferring the quartz boat into a tubular muffle furnace, raising the temperature to 700 ℃ at the heating rate of 5 ℃/min for carbonization, keeping the temperature at 700 ℃ for 2h, cooling to room temperature, and taking out to obtain the carbide.
(5) Washing and drying
Pouring 10g of carbonized product into 100mL of hydrochloric acid solution (HCl) with the concentration of 0.1 mol for washing, continuously washing after suction filtration for three times, and washing with pure water for three times until the pH value of an eluate is 6.84; drying the solid in a forced air drying oven at the drying temperature of 80 ℃ for 24 hours; ball-milling for 2 minutes, crushing, and sieving with a 100-mesh sieve to obtain the magnetic porous tea residue biochar.
The scanning electron microscope of the magnetic porous tea residue biochar prepared in the embodiment is shown in figure 1, and as shown in figure 1, the magnetic porous tea residue biochar has a developed pore structure and a large specific surface area. The specific surface area of the magnetic porous tea residue biochar is determined to be 1035 m2Per g, pore volume 0.5825 cm3The/g means that the magnetic porous tea residue biochar has stronger adsorption capacity on pollutants in the water body.
As shown in fig. 2, the magnetic porous tea residue biochar prepared in this example has a fourier-infrared spectrum 2 (FTIR), and as shown in fig. 2, the magnetic porous tea residue biochar contains rich functional groups, including hydroxyl groups, methyl groups, aromatic structures, carbon-oxygen functional groups, carbon-oxygen-carbon functional groups, iron-oxygen functional groups, and the like, and these functional groups are important reasons for the magnetic porous tea residue biochar to efficiently remove tetracycline from water.
Example 2
The specific preparation operation steps of the magnetic porous tea residue biochar for removing tetracycline in water are as follows:
(1) pretreatment of raw materials
Washing the waste tea leaves taken from a tea factory with water to remove impurities, putting the washed tea leaves into a forced air drying oven for drying, wherein the temperature of the forced air drying oven is 100 ℃, the time is 10 hours, and drying in the forced air drying oven; pulverizing with a pulverizer, sieving with 40 mesh sieve, and storing for use.
(2) Hydrothermal treatment
Mixing 3 g of tea leaves and 50 ml of pure water, putting the mixture into a hydrothermal reaction kettle, reacting for 10 hours at 200 ℃, and carrying out solid-liquid separation to obtain hydrothermal carbon; washing the hydrothermal carbon with absolute ethyl alcohol for three times; the ratio of the hydrothermal carbon to the absolute ethyl alcohol is 1: 20; and drying in a forced air drying oven at 100 ℃ for 8h to obtain the hydrothermal carbon.
(3) Dipping treatment of modifier
Heating water with charcoal: iron chloride: the potassium bicarbonate is prepared from the following raw materials in a mass ratio of 10g:10g:60g (1: 1: 6) of the raw materials are mixed, 200mL of pure water is added for immersion treatment, the mixture is stirred for 2 hours at the temperature of 25 ℃, and the mixture is put into an air-blast drying oven to be dried and removed of water, wherein the drying temperature is 100 ℃, and the drying time is 10 hours; obtaining the mixed solid of the hydrothermal carbon, the ferric chloride and the potassium bicarbonate.
(4) Charring and magnetizing treatment
And putting the mixed solid into a quartz boat, transferring the quartz boat into a tubular muffle furnace, raising the temperature to 700 ℃ at the heating rate of 5 ℃/min for carbonization, keeping the temperature at 700 ℃ for 1h, cooling to room temperature, and taking out to obtain the carbide.
(5) Washing and drying
Pouring 100mL of hydrochloric acid solution (HCl) with the concentration of 0.1 mol into 10g of carbide for washing, continuously washing after suction filtration for three times, and washing with pure water for three times until the pH value of an eluate is 7.15; drying the solid in a forced air drying oven at the drying temperature of 60 ℃ for 24 hours; ball-milling for 2 minutes, crushing, and sieving with a 100-mesh sieve to obtain the magnetic porous tea residue biochar.
The specific surface area of the magnetic porous tea residue biochar prepared in the example 2 is 965 m2Per g, pore volume 0.4219 cm3/g。
Example 3: application of magnetic porous tea residue biochar
In order to investigate the adsorption and application effects of the magnetic porous tea residue biochar, the following experiments were carried out: adding the magnetic porous tea residue biochar prepared in the embodiment into a water body containing tetracycline, adding 0.01 g of the magnetic porous tea residue biochar into 20 mL of the water body containing tetracycline, oscillating for 24h at room temperature, after oscillation adsorption is finished, adsorbing the composite material of the magnetic porous tea residue biochar by using a magnet, and separating the adsorbing material from water.
In the water body treatment process of the embodiment, 20 ml of tetracycline with different initial concentrations is added into a 50 ml centrifuge tube, the initial concentration of tetracycline is 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100mg/L, then 0.01 g of magnetic porous tea residue biochar is added into the centrifuge tube, after oscillation is carried out for 24h, the centrifuge tube is centrifuged for 5min under a centrifuge, the rotating speed is 4000 rpm, after centrifugation, the supernatant is filtered through a 0.45-micron filter membrane, the concentration of tetracycline in the supernatant is measured, and an ultraviolet spectrophotometer is adopted for measurement. The removal rate of the magnetic porous tea residue biochar to different tetracycline initial concentrations is calculated, and the result is shown in figure 3. Through determination, the magnetic porous tea residue biochar has higher adsorption rate to tetracycline in a certain concentration range (0-100mg/L), and when the initial concentration of the tetracycline in a water body is 10-50mg/L, the removal rate reaches 98%; when the initial concentration of the tetracycline in the water body is 60-100mg/L, the removal rate is over 95 percent, and the removal effect is obvious, which shows that the magnetic porous tea residue biochar has great potential for processing the tetracycline. In addition, the magnetic porous tea residue biochar after tetracycline adsorption is very convenient to recover, as shown in figure 4.
The ultraviolet spectrophotometer of this embodiment has a wavelength of 358nm and uses a quartz cuvette as the cuvette.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.

Claims (6)

1. A preparation method of magnetic porous tea residue biochar for removing tetracycline in water is characterized by comprising the following preparation operation steps:
(1) pretreatment of raw materials
Washing the tea leaves with hot water to remove impurities, caffeine and pigments in the tea leaves, washing the tea leaves until the tea leaves are colorless, drying the tea leaves, and crushing the tea leaves to obtain tea leaf powder;
(2) hydrothermal treatment
Mixing 3-5 g of tea leaves with 50-80 mL of pure water, reacting for 8-10 hours at 200 ℃ in a hydrothermal reaction kettle, carrying out solid-liquid separation, washing solids with an absolute ethyl alcohol solution for three times, and drying to obtain hydrothermal carbon;
(3) dipping treatment of modifier
Mixing hydrothermal carbon, ferric chloride and potassium bicarbonate according to a mass ratio of 10g:10g:60g, adding 200mL of pure water for immersion treatment, stirring for 2-4 h at the temperature of 15-35 ℃, and drying to obtain a mixed solid;
(4) charring and magnetizing treatment
Heating the mixed solid to 700 ℃ at a heating rate of 5 ℃/min in a tubular muffle furnace, carbonizing, keeping the temperature at 700 ℃ for 1-3 h, and cooling to room temperature to obtain a carbide;
(5) washing and drying
Washing the carbide in 100mL of 0.1 mol hydrochloric acid solution (HCl) with a concentration of 0.1 mol, performing suction filtration, washing and suction filtration for three times, washing with pure water until the pH value of an eluate is 6-8, drying, and performing ball milling treatment to obtain magnetic porous tea residue biochar;
the specific surface area of the magnetic porous tea residue biochar is 965-1035 m2Per gram, the pore volume is 0.4219-0.5825 cm3/g。
2. The preparation method of the magnetic porous tea residue biochar for removing tetracycline in the water body according to claim 1, which is characterized by comprising the following steps: in the step (1), the hot water is 80-100 ℃; the drying is carried out in a forced air drying oven at the temperature of 100-105 ℃; the crushing is carried out by crushing and sieving with a 40-mesh sieve.
3. The preparation method of the magnetic porous tea residue biochar for removing tetracycline in the water body according to claim 1, which is characterized by comprising the following steps: in the step (2), the solid and the absolute ethyl alcohol are mixed and washed according to the volume ratio of 1: 20.
4. The preparation method of the magnetic porous tea residue biochar for removing tetracycline in the water body according to claim 1, which is characterized by comprising the following steps: in the step (2), the step (3) and the step (5), the drying is drying in a forced air drying oven.
5. The preparation method of the magnetic porous tea residue biochar for removing tetracycline in the water body according to claim 1, which is characterized by comprising the following steps: and (5) performing ball milling, namely grinding for 2 minutes, and sieving by using a 100-mesh sieve.
6. The preparation method of the magnetic porous tea residue biochar for removing tetracycline in the water body according to claim 1, which is characterized by comprising the following steps: the adsorption rate of the magnetic porous tea residue biochar to tetracycline in the water body reaches 98% when the initial concentration of the tetracycline in the water body is 10-50 mg/L; when the initial concentration of the tetracycline in the water body is 60-100mg/L, the removal rate is more than 95%.
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