CN111992198A - Biomass charcoal material for catalytic degradation of antibiotics and preparation method thereof - Google Patents

Biomass charcoal material for catalytic degradation of antibiotics and preparation method thereof Download PDF

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CN111992198A
CN111992198A CN202010185716.9A CN202010185716A CN111992198A CN 111992198 A CN111992198 A CN 111992198A CN 202010185716 A CN202010185716 A CN 202010185716A CN 111992198 A CN111992198 A CN 111992198A
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biomass charcoal
antibiotics
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catalytic degradation
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李强
夏东升
张大捷
叶宇轩
万骏
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Wuhan Textile University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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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
    • B01J20/20—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
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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
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/10—Photocatalysts

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Abstract

The invention relates to a biomass charcoal material for catalyzing and degrading antibiotics and a preparation method thereof, wherein the preparation method of the biomass charcoal material comprises the following steps: (1) drying plant straws, crushing and sieving to obtain crushed materials; (2) adding nano titanium dioxide, ammonium ferric oxalate, nitrate and a coupling agent into water to obtain a steeping liquor; (3) adding the crushed material into the impregnation liquid, and stirring to obtain an impregnation material; (4) drying the impregnated material, then heating to 190-fold-210 ℃ in a horizontal quartz tube reactor in a nitrogen atmosphere, keeping the temperature for 1-3h, heating to 480-fold-520 ℃ for heat preservation and calcination for 4-6h, and cooling in the nitrogen atmosphere to obtain the catalyst. The method takes plant straws as raw materials, changes waste into valuable, can realize high-efficiency removal of antibiotics by utilizing biomass charcoal materials to perform catalytic degradation on the antibiotics, and has the advantages of simple treatment process, energy conservation, environmental protection, low cost, good removal effect and high recycling rate.

Description

Biomass charcoal material for catalytic degradation of antibiotics and preparation method thereof
Technical Field
The invention relates to the technical field of environment-friendly materials, in particular to a biomass charcoal material for catalyzing and degrading antibiotics and a preparation method thereof.
Background
The traditional carbon material is prepared by processing and treating coal, petroleum and the like serving as main raw materials, but the further development of the traditional carbon material is limited due to the global energy crisis and the deterioration of the ecological environment, and the important practical significance is achieved in developing renewable resources and converting the renewable resources into energy and various materials.
In recent years, with the development of modern agriculture and related processing industries, agricultural wastes are increasing. How to reasonably treat agricultural wastes is troubling people all the time, and meanwhile, the environmental problems brought by the agricultural wastes are more and more emphasized, so that the effective treatment of the agricultural wastes becomes a problem which needs to be solved urgently. However, agricultural wastes contain carbon-containing organic compounds such as sugars in a large amount, and thus can be used as renewable biomass resources. Therefore, the search for the utilization value of agricultural wastes is the best way to treat the agricultural wastes.
The biomass charcoal material is various charcoal materials prepared by using biomass as a raw material. Biomass refers to various organisms formed by photosynthesis, including all animals and plants and microorganisms. The biomass energy is the energy form that solar energy is stored in biomass in the form of chemical energy, namely the energy using biomass as a carrier. It is directly or indirectly derived from photosynthesis of green plants, can be converted into conventional solid, liquid and gaseous fuels, is inexhaustible, is a renewable energy source, and is a unique renewable carbon source. The carbon material is prepared by taking agricultural wastes as raw materials, so that the production cost of the carbon material can be reduced, waste is turned into wealth, and the sustainable development of the carbon material is realized.
Antibiotics have long been used in large quantities for the treatment of diseases in humans and animals and are added to animal feed in large therapeutic doses to prevent disease and promote growth in animals. However, most antibiotics are not completely absorbed by the body, and about 90% of the antibiotics are discharged into the ecological environment in the form of original or metabolite through the excrement and urine of patients and animals, and pollute soil and water body through different ways. At present, a large number of research reports on antibiotic substances detected in surface water and underground water are reported in countries such as canada, usa, uk, germany and china. The wastewater containing antibiotics is high-concentration organic wastewater with high biodegradation difficulty, high residue in the environment and strong biological toxicity. In recent years, due to the rapid development of the pharmaceutical industry, especially the appearance of antibiotics causes serious pollution to water resources in the world. The reasonable and effective treatment of antibiotic wastewater is urgent, which is a problem related to the development of society and the future living environment of human beings. The biomass charcoal material is used for treating sewage, and is a water pollution treatment mode with lower cost. The biomass contains special structural gaps, a large number of organic functional groups such as carboxyl, hydroxyl and the like are attached to the surface of the biomass, and after carbonization, the biomass retains the original good structural gaps of the biomass, has larger specific surface area, porosity and extremely strong adsorption force, but has poorer removal effect on antibiotics, lower adsorption capacity and no catalytic degradation capability. The preparation of biomass charcoal materials is reported more, such as: CN106276849A reports a preparation method of biomass charcoal material; CN106829923A reports a biomass charcoal material and a preparation method thereof; CN108905962A reports a preparation method of biomass charcoal adsorbing material. However, studies on the use of biomass charcoal materials for catalytic degradation of antibiotics have been rarely reported because the activity of biomass is easily lost in the process of becoming a charcoal material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a biomass charcoal material for catalyzing and degrading antibiotics and a preparation method thereof.
In order to realize the invention, the technical scheme is as follows:
a preparation method of biomass charcoal material for catalytic degradation of antibiotics comprises the following steps:
(1) drying plant straws, crushing and sieving to obtain crushed materials;
(2) adding nano titanium dioxide, ammonium ferric oxalate, nitrate and a coupling agent into water to obtain a steeping liquor;
(3) adding the crushed material into the impregnation liquid, and stirring to obtain an impregnation material;
(4) drying the impregnated material, then heating to 190-fold-210 ℃ in a horizontal quartz tube reactor in a nitrogen atmosphere, keeping the temperature for 1-3h, heating to 480-fold-520 ℃ for heat preservation and calcination for 4-6h, and cooling in the nitrogen atmosphere to obtain the catalyst.
Further, the preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying plant straws at the temperature of 70-100 ℃ until the water content is reduced to below 6 wt%, crushing and sieving with a 50-150 mesh sieve to obtain crushed materials;
(2) adding 1-2 parts by weight of nano titanium dioxide, 5-7 parts by weight of ammonium ferric oxalate, 2-3 parts by weight of nitrate and 1-2 parts by weight of coupling agent into 600 parts by weight of water to obtain impregnation liquid;
(3) adding the crushed material into an impregnation liquid, and stirring for 5-10h, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 10-50, so as to obtain an impregnation material;
(4) drying the impregnating material at the temperature of 90-100 ℃ for 40-50h, then heating to 190-140 ℃ at the speed of 8-12 ℃/min in a horizontal quartz tube reactor in nitrogen atmosphere, keeping the temperature for 1-3h, heating to 480-520 ℃ and calcining for 4-6h, and cooling in nitrogen atmosphere to obtain the catalyst.
Further, the plant straw in the step (1) is one of wheat straw, rice straw, corn straw or tobacco straw.
Further, the plant straw in the step (1) is rice straw.
Further, the nano titanium dioxide in the step (2) is rutile type nano titanium dioxide, and the particle size is 5-50 nm.
Further, in the step (2), the nitrate is strontium nitrate and/or cerium nitrate.
Further, the nitrate in the step (2) is composed of strontium nitrate and cerium nitrate according to the mass ratio of 1: 0.2-0.3.
Further, the coupling agent in the step (2) is a water-soluble titanate coupling agent.
Further, the preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 50-70 ℃, adjusting the pH to 6-7, controlling the rotation speed at 800-; introducing protective gas nitrogen, heating to 70-90 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed at 800-1200rpm, uniformly stirring, carrying out reflux reaction for 2-4h, then adding acrylic acid, continuing reflux reaction for 2-4h, stopping stirring, standing for 0.5-1.5h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 1.5-2.5.
The invention also provides a biomass charcoal material for catalyzing and degrading antibiotics, which is prepared by adopting the method.
The invention has the following remarkable characteristics:
(1) according to the biomass charcoal material prepared by the invention, because the ammonium ferric oxalate can generate steam and carbon dioxide at high temperature, the charcoal material can be subjected to hole expansion, so that the prepared charcoal material has the advantages of large specific surface area, strong adsorbability, uniform porous structure and the like; the carbon material has the double effects of catalytic degradation and adsorption.
(2) The water-soluble coupling agent in the preparation process can enhance the acting force between inorganic matters and straws, so that the material with catalytic activity is firmly attached to the surface of the biomass charcoal material, and the biomass charcoal material with high content, uniform dispersion and high catalytic performance can be prepared. The results of the examples show that: the addition of the water-soluble coupling agent obviously improves the capability of the biomass charcoal material in catalyzing and degrading antibiotics.
(3) The biomass charcoal material for catalytic degradation of antibiotics and the preparation method thereof provided by the invention have the advantages of simple treatment process, energy conservation, environmental protection, low cost, good removal effect and high repeated utilization rate, can realize effective and rapid degradation of antibiotics, and has good application prospect in practical treatment of antibiotic wastewater.
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FIG. 1 electron microscope image of biomass charcoal material for catalytic degradation of antibiotics prepared in example 1
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying rice straws at the temperature of 90 ℃ until the water content is 5 wt%, crushing and sieving by a 100-mesh sieve to obtain crushed materials;
(2) adding 1.5 parts by weight of rutile type nano titanium dioxide with the particle size of 10nm, 6 parts by weight of ammonium iron oxalate, 2.5 parts by weight of strontium nitrate and 1.5 parts by weight of water-soluble titanate coupling agent into 400 parts by weight of water to obtain impregnation liquid;
(3) adding the crushed material into an impregnation liquid, and stirring for 8 hours at a rotating speed of 300r/min, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 30, so as to obtain an impregnation material;
(4) drying the impregnated material at the temperature of 95 ℃ for 48h, then heating to 200 ℃ at the speed of 10 ℃/min in a horizontal quartz tube reactor in the nitrogen atmosphere, keeping the temperature for 2h, heating to 500 ℃ for heat preservation and calcination for 5h, and cooling in the nitrogen atmosphere to obtain the biomass charcoal material for catalytically degrading the antibiotic, wherein an electron microscope image of the biomass charcoal material for catalytically degrading the antibiotic is shown in figure 1.
The preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 60 ℃, adjusting the pH to 6.5, controlling the rotation speed to be 1000r/min, uniformly stirring, and carrying out reflux reaction for 1h for preheating; introducing protective gas nitrogen, heating to 80 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed to be 1000rpm, uniformly stirring, carrying out reflux reaction for 3h, then adding acrylic acid, continuing reflux reaction for 3h, stopping stirring, standing for 1h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 2.
Comparative example 1
Compared with example 1, the only difference is that "1.5 parts by weight of rutile type nano titanium dioxide having a particle size of 10nm, 6 parts by weight of ferric ammonium oxalate, 2.5 parts by weight of strontium nitrate, 1.5 parts by weight of water-soluble titanate coupling agent were added to 400 parts by weight of water" was replaced with "1.5 parts by weight of rutile type nano titanium dioxide having a particle size of 10nm, 6 parts by weight of ferric ammonium oxalate, 2.5 parts by weight of strontium nitrate were added to 400 parts by weight of water".
The preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying rice straws at the temperature of 90 ℃ until the water content is 5 wt%, crushing and sieving by a 100-mesh sieve to obtain crushed materials;
(2) adding 1.5 parts by weight of rutile type nano titanium dioxide with the particle size of 10nm, 6 parts by weight of ferric ammonium oxalate and 2.5 parts by weight of strontium nitrate into 400 parts by weight of water to obtain an impregnation solution;
(3) adding the crushed material into an impregnation liquid, and stirring for 8 hours at a rotating speed of 300r/min, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 30, so as to obtain an impregnation material;
(4) drying the impregnated material at the temperature of 95 ℃ for 48h, then heating to 200 ℃ at the speed of 10 ℃/min in a horizontal quartz tube reactor in the nitrogen atmosphere, keeping the temperature for 2h, heating to 500 ℃ for heat preservation and calcination for 5h, and cooling in the nitrogen atmosphere to obtain the biomass carbon material for catalytic degradation of antibiotics.
The preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 60 ℃, adjusting the pH to 6.5, controlling the rotation speed to be 1000r/min, uniformly stirring, and carrying out reflux reaction for 1h for preheating; introducing protective gas nitrogen, heating to 80 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed to be 1000rpm, uniformly stirring, carrying out reflux reaction for 3h, then adding acrylic acid, continuing reflux reaction for 3h, stopping stirring, standing for 1h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 2.
Example 2
The preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying rice straws at the temperature of 90 ℃ until the water content is 5 wt%, crushing and sieving by a 100-mesh sieve to obtain crushed materials;
(2) adding 1.5 parts by weight of rutile type nano titanium dioxide with the particle size of 10nm, 6 parts by weight of ammonium iron oxalate, 2.5 parts by weight of cerium nitrate and 1.5 parts by weight of water-soluble titanate coupling agent into 400 parts by weight of water to obtain impregnation liquid;
(3) adding the crushed material into an impregnation liquid, and stirring for 8 hours at a rotating speed of 300r/min, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 30, so as to obtain an impregnation material;
(4) drying the impregnated material at the temperature of 95 ℃ for 48h, then heating to 200 ℃ at the speed of 10 ℃/min in a horizontal quartz tube reactor in the nitrogen atmosphere, keeping the temperature for 2h, heating to 500 ℃ for heat preservation and calcination for 5h, and cooling in the nitrogen atmosphere to obtain the biomass carbon material for catalytic degradation of antibiotics.
The preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 60 ℃, adjusting the pH to 6.5, controlling the rotation speed to be 1000r/min, uniformly stirring, and carrying out reflux reaction for 1h for preheating; introducing protective gas nitrogen, heating to 80 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed to be 1000rpm, uniformly stirring, carrying out reflux reaction for 3h, then adding acrylic acid, continuing reflux reaction for 3h, stopping stirring, standing for 1h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 2.
Example 3
The preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying the wheat straws at the temperature of 90 ℃ until the water content is 5 wt%, crushing and sieving by a 100-mesh sieve to obtain crushed materials;
(2) adding 1.5 parts by weight of rutile type nano titanium dioxide with the particle size of 10nm, 6 parts by weight of ammonium iron oxalate, 2.5 parts by weight of strontium nitrate and 1.5 parts by weight of water-soluble titanate coupling agent into 400 parts by weight of water to obtain impregnation liquid;
(3) adding the crushed material into an impregnation liquid, and stirring for 8 hours at a rotating speed of 300r/min, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 30, so as to obtain an impregnation material;
(4) drying the impregnated material at the temperature of 95 ℃ for 48h, then heating to 200 ℃ at the speed of 10 ℃/min in a horizontal quartz tube reactor in the nitrogen atmosphere, keeping the temperature for 2h, heating to 500 ℃ for heat preservation and calcination for 5h, and cooling in the nitrogen atmosphere to obtain the biomass carbon material for catalytic degradation of antibiotics.
The preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 60 ℃, adjusting the pH to 6.5, controlling the rotation speed to be 1000r/min, uniformly stirring, and carrying out reflux reaction for 1h for preheating; introducing protective gas nitrogen, heating to 80 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed to be 1000rpm, uniformly stirring, carrying out reflux reaction for 3h, then adding acrylic acid, continuing reflux reaction for 3h, stopping stirring, standing for 1h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 2.
Example 4
The preparation method of the biomass charcoal material for catalyzing and degrading the antibiotics comprises the following steps:
(1) drying rice straws at the temperature of 90 ℃ until the water content is 5 wt%, crushing and sieving by a 100-mesh sieve to obtain crushed materials;
(2) adding 1.5 parts by weight of rutile type nano titanium dioxide with the particle size of 10nm, 6 parts by weight of ammonium iron oxalate, 2.5 parts by weight of nitrate and 1.5 parts by weight of water-soluble titanate coupling agent into 400 parts by weight of water to obtain impregnation liquid; the nitrate consists of strontium nitrate and cerium nitrate according to the mass ratio of 1: 0.25;
(3) adding the crushed material into an impregnation liquid, and stirring for 8 hours at a rotating speed of 300r/min, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 30, so as to obtain an impregnation material;
(4) drying the impregnated material at the temperature of 95 ℃ for 48h, then heating to 200 ℃ at the speed of 10 ℃/min in a horizontal quartz tube reactor in the nitrogen atmosphere, keeping the temperature for 2h, heating to 500 ℃ for heat preservation and calcination for 5h, and cooling in the nitrogen atmosphere to obtain the biomass carbon material for catalytic degradation of antibiotics.
The preparation method of the water-soluble titanate coupling agent comprises the following steps: putting 1, 3-propylene glycol into a container at 60 ℃, adjusting the pH to 6.5, controlling the rotation speed to be 1000r/min, uniformly stirring, and carrying out reflux reaction for 1h for preheating; introducing protective gas nitrogen, heating to 80 ℃, slowly adding tetraisopropyl titanate, controlling the rotation speed to be 1000rpm, uniformly stirring, carrying out reflux reaction for 3h, then adding acrylic acid, continuing reflux reaction for 3h, stopping stirring, standing for 1h, cooling to room temperature, and transferring to a beaker to obtain the titanate coupling agent. The mol ratio of the 1, 3-propylene glycol, the tetraisopropyl titanate and the acrylic acid is 1: 2.
Test example
50mg of the biomass charcoal material for catalyzing and degrading the antibiotics prepared in the examples 1-6 and the comparative example 1 is added into 100mL of tetracycline solution with the concentration of 20mg/L, the mixture is subjected to uniform ultrasonic treatment, the mixture is subjected to reaction for 60min (magnetic stirring) under the condition of no light, after adsorption and desorption balance is achieved, the mixture is subjected to photocatalytic degradation reaction under the condition of visible light with the wavelength lambda of more than 420nm for 150min, and the photocatalytic degradation of the tetracycline in the water body is completed. After the photocatalytic degradation reaction is finished, collecting the residual sample, drying, and carrying out photocatalytic degradation on the tetracycline water body under the same experimental conditions for 4 times in total. Sampling 3mL every 30min, measuring the characteristic peak value of tetracycline in the solution by using an ultraviolet-visible spectrophotometer, converting the characteristic peak value into concentration, calculating degradation rates of different cycles, and taking an average value. Specific results are shown in table 1.
Table 1: test result table
A degradation rate%
Example 1 92.1
Example 2 91.6
Example 3 94.4
Example 4 97.7
Comparative example 1 57.3
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (8)

1. A preparation method of biomass charcoal material for catalytic degradation of antibiotics is characterized by comprising the following steps:
(1) drying plant straws, crushing and sieving to obtain crushed materials;
(2) adding nano titanium dioxide, ammonium ferric oxalate, nitrate and a coupling agent into water to obtain a steeping liquor;
(3) adding the crushed material into the impregnation liquid, and stirring to obtain an impregnation material;
(4) drying the impregnated material, then heating to 190-fold-210 ℃ in a horizontal quartz tube reactor in a nitrogen atmosphere, keeping the temperature for 1-3h, heating to 480-fold-520 ℃ for heat preservation and calcination for 4-6h, and cooling in the nitrogen atmosphere to obtain the catalyst.
2. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 1, wherein:
(1) drying plant straws at the temperature of 70-100 ℃ until the water content is reduced to below 6 wt%, crushing and sieving with a 50-150 mesh sieve to obtain crushed materials;
(2) adding 1-2 parts by weight of nano titanium dioxide, 5-7 parts by weight of ammonium ferric oxalate, 2-3 parts by weight of nitrate and 1-2 parts by weight of coupling agent into 600 parts by weight of water to obtain impregnation liquid;
(3) adding the crushed material into an impregnation liquid, and stirring for 5-10h, wherein the mass ratio of the crushed material to the impregnation liquid is 1: 10-50, so as to obtain an impregnation material;
(4) drying the impregnating material at the temperature of 90-100 ℃ for 40-50h, then heating to 190-140 ℃ at the speed of 8-12 ℃/min in a horizontal quartz tube reactor in nitrogen atmosphere, keeping the temperature for 1-3h, heating to 480-520 ℃ and calcining for 4-6h, and cooling in nitrogen atmosphere to obtain the catalyst.
3. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 1 or 2, wherein: the plant straw is one of wheat straw, rice straw, corn straw or tobacco straw.
4. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 3, wherein: the plant straw is rice straw.
5. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 1 or 2, wherein: the nano titanium dioxide is rutile type nano titanium dioxide, and the particle size is 5-50 nm.
6. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 1 or 2, wherein: the nitrate is strontium nitrate and/or cerium nitrate.
7. The method for preparing biomass charcoal material for catalytic degradation of antibiotics according to claim 1 or 2, wherein: the coupling agent is a water-soluble titanate coupling agent.
8. A biomass charcoal material for catalyzing and degrading antibiotics is characterized in that: prepared by the method of any one of claims 1 to 7.
CN202010185716.9A 2020-03-17 2020-03-17 Biomass charcoal material for catalytic degradation of antibiotics and preparation method thereof Pending CN111992198A (en)

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