CN113998771B

CN113998771B - TPhP degradation method, biochar-inorganic mineral complex material and preparation method thereof

Info

Publication number: CN113998771B
Application number: CN202111645926.2A
Authority: CN
Inventors: 于云江; 常兆峰; 钟紫娟; 郭浩博; 向明灯; 李红艳
Original assignee: South China Institute of Environmental Science of Ministry of Ecology and Environment
Current assignee: South China Institute of Environmental Science of Ministry of Ecology and Environment
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2022-03-25
Anticipated expiration: 2041-12-30
Also published as: CN113998771A

Abstract

The invention discloses a TPhP degradation method, a biochar-inorganic mineral complex material and a preparation method thereof, wherein the TPhP degradation method comprises the following steps: s1: preparing an N-doped biochar-inorganic mineral composite material; s2: measuring the concentration of TPhP in the sewage and the degradation rate of the prepared composite material, and calculating the amount of the composite material required by degradation; s3: adding PDS into the sewage water body, adjusting the concentration of the PDS to a preset value, adding the composite material, stirring or oscillating for reaction for 4-8 hours to enable the composite material to catalyze and activate the PDS, and adsorbing and degrading TPhP in the water body; s4: and (4) determining the concentration of TPhP in the treated water body, and repeating the steps S2-S3 if the concentration of TPhP in the treated water body does not reach the standard. The invention also provides a biochar-inorganic mineral composite material and a preparation method thereof. The method and the material provided by the invention have the advantages of simple process, wide sources, environmental friendliness, high efficiency and low cost, and can meet the requirements of large-scale popularization and application.

Description

TPhP degradation method, biochar-inorganic mineral complex material and preparation method thereof

Technical Field

The invention belongs to the technical field of sewage treatment and environmental protection, and particularly relates to a method for degrading TPhP in a water body, a biochar-inorganic mineral complex material and a preparation method thereof.

Background

Organic Phosphate Esters (OPEs) are used as important members of phosphorus flame retardants to replace bromine flame retardants and are widely applied to production practice. During production, processing and product use, the substances can enter various environmental media in various forms, become environmental pollutants and pose potential threats to ecology and human health. Research indicates that OPEs have biological toxicity such as carcinogenicity, mutagenicity, neurotoxicity and genetic toxicity. In order to avoid and reduce the health risk of OPEs, it is important to thoroughly clean the environment of OPEs in addition to controlling the emissions of OPEs from the source.

Triphenyl phosphate (TPhP) is one of the organophosphorus flame retardants, and is often used as a fire retardant additive or plasticizer. TPhP is used in large amount and is continuously detected in different environment mediums, and the environmental risk thereof is gradually paid attention to people. The research shows that TPhP has biological toxicity such as neurotoxicity, carcinogenicity and developmental toxicity. TPhP, as a strongly lipophilic OPE, is more readily absorbed by organisms after entering the environment than a hydrophilic OPE, thereby causing greater biological toxicity. However, TPhP cannot be effectively removed in a wastewater treatment process. There is therefore a need to find efficient, rapid and economical methods and techniques for treating TPhP in aqueous environments.

At present, the TPhP pollution of a water body is repaired, and the degradation of OPEs in the environment is mainly depended on the microbial degradation, for example, one sphingosine bacterium capable of degrading triphenyl phosphate disclosed in Chinese patent application CN110643534A can degrade 100mg/L TPhP in inorganic salt by 99.7% within 24 hours. However, microbial degradation generally has the defects of low degradation efficiency, long degradation period, high cost, easy interference of external environmental conditions (temperature, pH value and the like), unstable treatment effect and the like.

In addition, there is a treatment method using chemical materials for catalytic degradation in the prior art, for example, a technical scheme disclosed in chinese patent application CN111013590A for using a supported biochar catalytic material for degradation of triphenyl phosphate (TPhP) wastewater, wherein the preparation method of the biochar supported tricobalt tetroxide catalytic material used in the method is as follows: firstly, obtaining a hydrothermal carbon-loaded cobalt material, then filtering, washing and drying the hydrothermal carbon-loaded cobalt material, putting the hydrothermal carbon-loaded cobalt material into a muffle furnace for pyrolysis, and grinding the hydrothermal carbon-loaded cobalt material to obtain the biocarbon-loaded cobaltosic oxide catalytic material. However, the cobalt material adopted in the method is expensive and harmful to the environment, and the material preparation process is complex and high in cost, so that the method is not beneficial to large-scale popularization and application.

Therefore, the research on a TPhP chemical degradation method and a TPhP chemical degradation material which have the advantages of high degradation speed, small environmental influence on degradation, stable treatment effect, environmental friendliness and low cost can meet the popularization and application requirements of large range and low cost.

Disclosure of Invention

In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a method for degrading TPhP in water, which employs an environmentally friendly N-doped biochar-inorganic mineral composite material as an adsorbent and an activator, and catalyzes peroxydisulfate PDS based on the iron-based biochar composite material to generate hydroxyl radicals (HO.) and sulfate radicals (SO 4) with strong oxidizing properties in advanced oxidation treatment processes (AOPs)^•-) TPhP in the water body is adsorbed and degraded, N-doped biochar provides a nitrogen source for the degradation reaction process, degradation conditions are optimized, the effects of high degradation speed, small environmental influence on degradation, wide material sources, stable treatment effect and low cost are achieved, the degradation rate of TPhP (triphenyl phosphate) in the water body reaches more than 85% within 8 hours, and the popularization and application requirements of large range and low cost can be met;

the invention also aims to provide the N-doped biochar-inorganic mineral complex material for implementing the method and the preparation method thereof, wherein the biochar-inorganic mineral complex is prepared by a diffusion mechanism and a self-propagating high-temperature synthesizer, and the biochar is prepared by using a raw material with high nitrogen content, so that the self-source nitrogen doping is realized on the premise of not adding an external chemical reagent; the three materials are simultaneously modified by adopting a mechanical ball milling modification method, so that the preparation process is simplified, and the material bonding performance is improved.

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

a method for degrading TPhP, comprising the steps of:

s1: preparing an N-doped biochar-inorganic mineral composite material, which comprises the following steps: fe₂O₃@ MBC or FeO (OH) @ MBC, wherein TPhP is triphenyl phosphate, and MBC is N-doped charcoal;

s2: measuring the concentration of TPhP in the sewage and the degradation rate of the prepared composite material, and calculating the dosage of the N-doped biochar-inorganic mineral composite material required by degradation;

s3: when the pH initial value of the water body is 6-9, adjusting the concentration of the water body to 10-12 mmol/L without adjusting, adding an N-doped biochar-inorganic mineral composite material, stirring or oscillating for 4-8 h to enable the N-doped biochar-inorganic mineral composite material to catalyze and activate the PDS, adsorbing and degrading TPhP in the water body, and providing a nitrogen source for the degradation reaction process by the N-doped biochar;

s4: and (4) determining the concentration of TPhP in the treated water body, and repeating the steps S2-S3 if the concentration of TPhP in the treated water body does not reach the standard.

The adding amount of the N-doped biochar-inorganic mineral composite material in the step S3 is 0.1-0.25 g/L;

the N-doped biochar MBC is self-derived nitrogen-doped biochar;

said Fe₂O₃In @ MBC, MBC is combined with Fe₂O₃The mass ratio of (1): (0.33-2);

in the FeO (OH) @ MBC, the mass ratio of MBC to FeO (OH) is 1: (0.33-2);

the N-doped biochar-inorganic mineral composite material for implementing the TPhP degradation method is characterized by being ball-milled and modified Fe₂O₃@ MBC or FeO (OH) @ MBC, wherein MBC is self-derived N-doped biochar, and is mixed with Fe₂O_3、One of the FeO (OH) powders is simultaneously ball-milled and modified.

The preparation method of the N-doped biochar-inorganic mineral composite material is characterized by comprising the following steps of:

m1: preparing N-doped biochar MBC:

washing poultry feather with ultrapure water, and drying in an oven at 60 ℃;

wrapping a proper amount of feather biomass with tinfoil paper, and placing the feather biomass in a vacuum tube furnace for carbonization, wherein the temperature rise procedure of the vacuum tube furnace is as follows: heating from room temperature to 350 ℃ at a speed of 10 ℃/min, keeping for 2h, then cooling from 350 ℃ to 75 ℃ at a speed of 10 ℃/min to obtain a primary pyrolytic biochar material, and taking out for later use;

carrying out secondary pyrolysis by taking the primary pyrolysis biochar material as a raw material, heating the raw material to 350 ℃, 500 ℃, 650 ℃ and 800 ℃ at a speed of 10 ℃/min, keeping the temperature for 2h, and then cooling the raw material to 75 ℃ at a speed of 10 ℃/min, so as to correspondingly prepare four kinds of self-derived N-doped biochar MBC with the pyrolysis conditions of 350 ℃, 500 ℃, 650 ℃ and 800 ℃;

m2: preparing an N-doped biochar-inorganic mineral composite material:

separately prepared from hematite Fe₂O₃And goethite FeO (OH) powder;

weighing any one of the self-derived N-doped biochar MBC and inorganic mineral (Fe) in sequence according to a set mass ratio₂O₃Or one of FeO (OH) powder) is subjected to ball milling modification, and N is doped with biochar MBC and Fe₂O₃Or one of FeO (OH) powder is simultaneously placed in a ball milling tank, clockwise rotation is carried out for 2h at one of the rotation speeds of 350r/min, 500r/min and 650r/min respectively, then operation is stopped for 30 min, and anticlockwise rotation is carried out for 2h at the same rotation speed; repeating the processes of clockwise rotation, stop operation and anticlockwise rotation for several times respectively to enable the time accumulation of ball milling rotation to reach 4h, 6h and 12h respectively and enable Fe₂O₃And goethite FeO (OH) powder and N-doped biochar MBC are mutually combined, and the N-doped biochar MBC and Fe are₂O₃And goethite FeO (OH) are modified simultaneously, namely, a plurality of N-doped biochar-inorganic mineral composite materials under different preparation conditions are prepared respectively.

The poultry feather in the step M1 is one of chicken feather, duck feather, goose feather or a mixture thereof with the nitrogen content of more than 10wt% after carbonization.

In the step M2, the mass ratio of the N-doped biochar MBC to the inorganic mineral is respectively as follows: 1:2, 1:1, 2:1 and 3: 1.

In the ball milling modification of the step M2, the mass ratio of the total mass of the biochar and the inorganic mineral to the grinding balls is respectively: 1:10, 1:50, 1: 100.

Compared with the prior art, the invention has the advantages that:

1. the invention provides a method for degrading TPhP in water, which applies nitrogen-doped biochar and a nitrogen-doped biochar-inorganic mineral complex material system to degrading organic phosphate in water environment, and optimizes degradation conditions in multiple ways to improve the degradation rateThe efficiency of degradation of the material system and the reduction of the consumption of the material system. The invention specifically adopts an environment-friendly N-doped biochar-inorganic mineral composite material as an adsorbent and an activator, and generates hydroxyl free radicals (HO.) and sulfate free radicals (SO 4) with strong oxidizing property in advanced oxidation treatment processes (AOPs) based on the catalysis of PDS by the iron-based biochar composite material^•-) TPhP in the water body is adsorbed and degraded, N-doped biochar provides a nitrogen source for the degradation reaction process, the effects of high degradation speed, small environmental influence on degradation, wide material sources, stable treatment effect and low cost are achieved, the degradation rate of TPhP (triphenyl phosphate) in the water body within 8 hours reaches more than 85%, and the popularization and application requirements of large range and low cost can be met.

2. According to the N-doped biochar-inorganic mineral complex material for implementing the method and the preparation method thereof, the biochar-inorganic mineral complex is prepared through a diffusion mechanism and a self-propagating high-temperature synthesizer, and biochar is prepared by using a raw material with high nitrogen content, so that self-source nitrogen doping is realized on the premise of not adding an external chemical reagent; the proportion of nitrogen in the biochar is improved by adopting a secondary pyrolysis method, and more graphite nitrogen and pyridine nitrogen are generated; meanwhile, the three materials are modified pairwise by adopting a mechanical ball milling modification method, so that the preparation process is simplified, and the bonding performance of the materials is improved.

3. According to the N-doped biochar-inorganic mineral composite material for implementing the method and the preparation method thereof, the self-derived nitrogen plays an important role in the TPhP degradation process. The mass ratio of the N-doped biochar is more than 10wt%, and a sufficient nitrogen source can be provided for longer-time degradation. Because the electronegativity of nitrogen in the biochar is higher than that of carbon, high-content nitrogen in the biochar-inorganic mineral complex can absorb electrons on adjacent carbon atoms to enable the electrons to be positively charged, so that the charge distribution of the original carbon plane is changed, pi electrons on the carbon atoms are activated, the electron transfer capacity of the carbon surface is improved, and persulfate activation is promoted. After the degradation reaction, the contents of graphite nitrogen and pyridine nitrogen on the complex are obviously reduced, which shows that the nitrogen in the two forms plays an important role in the TPhP degradation process. Compared with nitrogen in other forms, the self-source nitrogen provided by the invention has smaller covalent radius and higher electronegativity, and has stronger electron-withdrawing ability, while the pyridine nitrogen improves the initial potential of the complex. The excellent properties of the N-doped biochar are beneficial to the transfer of electrons between the complex and persulfate, so that the activation of persulfate to generate free radicals is accelerated, and TPhP is degraded.

4. The invention provides a degradation method and a material system, which make full use of biochar and transition metal inorganic minerals (hematite (Fe)₂O₃) And goethite (feo (oh)) have great potential in degrading organic pollutants while overcoming the obvious drawbacks of the two when applied separately. For example, biochar particles are small and dispersed and are difficult to separate after application in an ambient medium. The iron oxide can activate hydrogen peroxide, persulfate and the like to generate free radicals, and oxidize and degrade organic pollutants; however, the reactivity is lowered because of small particle size, high surface energy, and easy occurrence of agglomeration. The two inorganic minerals have wide sources and low cost, and the two N-doped biochar-inorganic mineral composite materials prepared from the two inorganic minerals have similar performance and price, and can be directly used as equivalent substitutes in use.

5. The invention provides a degradation method and a material system, wherein biochar is used as a porous carbon carrier, and a composite material prepared by one of two iron oxides is loaded respectively, so that the agglomeration of the iron oxides can be prevented, the redox active point position of the biochar can be increased, and the catalytic degradation performance of the biochar on organic pollutants is enhanced. In addition, nitrogen atoms (N) are doped, so that the surface defects and catalytic sites of the biochar can be increased, the electron transfer rate is improved, and PDS activation and pollutant degradation are promoted. In the prior art, the preparation and N doping of the biochar-inorganic mineral composite material are generally realized through chemical coprecipitation and the addition of an exogenous chemical reagent, which undoubtedly causes the pollution of the exogenous chemical reagent to the environment and the complication of the preparation process. Therefore, the method for preparing the composite material by adopting the raw material with high nitrogen content and being simple and convenient to clean better solves the problems. The invention takes poultry feather (such as chicken feather, the content of N is more than 13 percent) as raw material, saves the working procedure of additionally providing nitrogen source and nitrogen, greatly improves the material performance, and simplifies the preparation process and the material cost.

6. The invention provides a degradation method and a material system, wherein a biochar-inorganic mineral complex is prepared by a mechanical ball milling method through a diffusion mechanism and a self-propagating high-temperature synthesis mechanism (see figure 2), and the material is further applied to a degradation system of organic phosphate to verify the effectiveness of the material. The ball milling method adopted by the invention is a powder solid state combination (alloy) method under a non-equilibrium state. The mechanism mainly includes diffusion mechanism and self-propagating high temperature synthesis (SHS) mechanism. The diffusion-type mechanism means that diffusion always occurs in a direction in which the gibbs free energy decreases during diffusion. In order to achieve atomic transitions, the system needs to reach a certain energy state, this extra energy is called activation energy Δ Ea, while atomic transitions in the solid state are generally considered to be vacancy mechanisms, the activation energy of which is the sum of both vacancy formation energy Δ Ef and migration energy Δ Em. The solid state reaction induced by mechanical alloying during high energy ball milling is actually a result of the combined effect of defect energy and collision energy. Therefore, it no longer requires the energy for vacancy formation and the total activation energy required for diffusion is reduced. The self-propagating high-temperature synthesis (SHS) mechanism refers to a technique for synthesizing materials by self-heating and self-conduction of high chemical reaction heat between reactants, and when the reactants are ignited, they automatically propagate toward the unreacted area until the reaction is completed.

7. The invention provides a degradation method and a material system, which mainly adopts biochar and an iron-based material to repair TPhP pollution of a water body, has wide raw material sources and low price, and has the advantages of easily obtained materials, simple process, less total material consumption, high degradation speed, small pH influence (no need of adjustment when the initial pH value of a naturally adopted water body is 6-9) and the like compared with the microorganism and biochar loaded cobaltosic oxide catalytic material and the like in the prior art. The comprehensive treatment cost of sewage remediation is favorable for large-area popularization and application. Through actual prediction calculation and verification, the comprehensive repair cost of the invention is only 30% of that of the prior art for the same polluted water body repair.

8. According to the degradation method and the material system provided by the invention, the biochar-inorganic mineral composite material can be recycled. But considering that the recycling cost is high, the material is environment-friendly, easy to prepare and low in cost, and does not need to be recycled under the condition of no special requirement so as to save the cost.

Drawings

FIG. 1 shows an example of an N-doped biochar-inorganic mineral composite material Fe₂O₃Scanning electron micrographs of @ MBC;

FIG. 2 is a schematic diagram of the mechanical ball milling modification principle of the N-doped biochar-inorganic mineral composite material according to the embodiment of the invention;

FIGS. 3-6 show Fe prepared from various self-derived N-doped biochar MBCs obtained at different secondary pyrolysis temperatures in example 2 of the present invention₂O₃The schematic diagram of the relationship between the change of the @ MBC or FeO (OH) @ MBC composite material and the degradation rate;

FIGS. 7 to 9 show Fe in example 3 of the present invention₂O₃The schematic diagram of the change relationship between the rotating speed and the degradation rate when the @ MBC or FeO (OH) MBC ball milling preparation is carried out;

FIGS. 10 to 12 show Fe in example 4 of the present invention₂O₃The time length of the @ MBC or FeO (OH) @ MBC ball milling is continuous and the change relation of the degradation rate is shown schematically;

FIGS. 13 to 15 are Fe at the time of ball-milling modification in example 5 of the present invention₂O₃The mass ratio of @ MBC or FeO (OH) @ MBC to the grinding balls (ball milling ratio) and the change relation of the degradation rate are shown schematically;

FIGS. 16 to 19 are schematic diagrams showing the relationship between the mass ratio of biochar to inorganic mineral and the degradation rate in example 6 of the present invention;

FIGS. 20 to 24 show Fe in example 7 of the present invention₂O₃The amount (concentration) of @ MBC or FeO (OH) @ MBC added and the degradation rate are shown in the graph;

FIGS. 25-29 are graphs showing the variation of the amount (concentration) of PDS added and the degradation rate in example 8 of the present invention;

FIGS. 30-34 are graphs showing the relationship between different pH values and degradation rates in example 9 of the present invention.

Detailed Description

The invention is explained in detail below with reference to the figures and examples:

example 1:

referring to the attached fig. 1 and fig. 2, the present example provides an N-doped biochar-inorganic mineral composite material for implementing a TPhP (triphenyl phosphate) degradation method, which is ball-milling modified Fe₂O₃@ MBC or one of FeO (OH) @ MBC, wherein the MBC is self-derived N-doped biochar and is mixed with inorganic mineral Fe₂O₃Or FeO (OH) powder is subjected to simultaneous ball milling modification.

Referring to FIG. 1, the Fe₂O₃The microstructure characteristic change of the material of @ MBC (or FeO (OH) @ MBC) is more obvious compared with the traditional biochar material. In the process of preparing the biochar-inorganic mineral by ball milling, the original carbon skeleton structure of the biochar is broken, so that the particle size of the biochar is reduced and the biochar is in an irregular flaky fragment structure, the surface of the fragment structure is rough, and more active sites can be exposed in the process of catalytically degrading TPhP. Inorganic mineral Fe₂O₃Or FeO (OH) is bonded on the surface of the biochar fragment structure through Fe-O and Fe-OH chemical bonds and passes through Fe in the process of catalytic reaction²⁺/Fe³⁺The TPhP is degraded by the conversion and catalysis of persulfate to generate free radicals.

The preparation method of the N-doped biochar-inorganic mineral composite material provided by the embodiment comprises the following steps:

m1: preparing N-doped biochar MBC:

the feather of the poultry (chicken feather is used in the embodiment) is washed clean by ultrapure water and is put into an oven to be dried at 60 ℃;

wrapping a proper amount of chicken feather biomass with tinfoil paper, and placing the chicken feather biomass in a vacuum tube furnace for carbonization, wherein the temperature rise procedure of the vacuum tube furnace is as follows: heating from room temperature to 350 ℃ at a speed of 10 ℃/min, keeping for 2h, then cooling from 350 ℃ to 75 ℃ at a speed of 10 ℃/min to obtain a primary pyrolytic biochar material, and taking out for later use;

carrying out secondary pyrolysis by taking the primary pyrolysis biochar material as a raw material, heating the raw material to 350 ℃, 500 ℃, 650 ℃ and 800 ℃ at the room temperature of 10 ℃/min, keeping the temperature for 2h, and then cooling the raw material to 75 ℃ from 350 ℃, 500 ℃, 650 ℃ and 800 ℃ at the room temperature of 10 ℃/min, so as to correspondingly prepare four kinds of self-derived N-doped biochar MBC with the pyrolysis conditions of 500 ℃, 650 ℃ and 800 ℃;

m2: preparing an N-doped biochar-inorganic mineral composite material:

separately prepared from hematite Fe₂O₃Or an inorganic mineral made of goethite FeO (OH) powder;

weighing any one of the self-derived N-doped biochar MBC and inorganic mineral (Fe) in sequence according to a set mass ratio₂O₃Or one of goethite FeO (OH) powder) is subjected to ball milling modification, and N-doped biochar MBC and Fe₂O₃Or one of goethite FeO (OH) powder is simultaneously placed in a ball milling tank, clockwise rotation is carried out for 2h at one of the rotation speeds of 350r/min, 500r/min and 650r/min respectively, then operation is stopped for 30 min, and anticlockwise rotation is carried out for 2h at the same rotation speed; repeating the processes of clockwise rotation, stop operation and anticlockwise rotation for several times respectively to enable the time accumulation of ball milling rotation to reach 4h, 6h and 12h respectively and enable Fe to be respectively₂O₃Combined with goethite FeO (OH) powder and N-doped biochar MBC, and the N-doped biochar MBC and Fe₂O₃Or the goethite FeO (OH) powder is modified simultaneously, namely, a plurality of N-doped biochar-inorganic mineral composite materials under different preparation conditions are respectively prepared.

The poultry feather in the step M1 is one of chicken feather, duck feather, goose feather or a mixture thereof, the nitrogen content of which is more than 10wt% after pyrolysis and carbonization. In this example, chicken feathers were used, the nitrogen content of which after the secondary pyrolysis was greater than 13 wt%.

In the step M2, the mass ratio of the N-doped biochar MBC to the inorganic mineral is respectively as follows: 1:2, 1:1, 2:1 and 3: 1;

in the ball milling modification of the step M2, the biochar is mixed with inorganic minerals (namely Fe)₂O₃Total mass of @ MBC or FeO (OH) @ MBC), mass ratio to grinding ballRespectively as follows: 1:10, 1:50, 1: 100.

The method for degrading TPhP provided by the embodiment comprises the following steps:

s1: preparing an N-doped biochar-inorganic mineral composite material, which is prepared by the following steps: fe₂O₃@ MBC or one of FeO (OH) @ MBC, wherein MBC is N-doped biochar;

s3: adding PDS into the sewage water body, adjusting the concentration of the PDS to a preset value, and adding an N-doped biochar-inorganic mineral complex material (Fe)₂O₃One of @ MBC or FeO (OH) @ MBC, which can be replaced with each other equally, and the adding amount is 0.1-0.25 g/L; stirring or oscillating for 4-8 h to enable the N-doped biochar-inorganic mineral complex material to catalyze and activate PDS, adsorbing and degrading TPhP in the water body, wherein the N-doped biochar provides a nitrogen source for the degradation reaction process; when the pH value of the naturally sampled water body is 6-9, adjustment is not needed;

The N-doped biochar MBC is self-derived nitrogen-doped biochar prepared by thermally insulating and carbonizing poultry feathers.

Said Fe₂O₃In @ MBC, MBC is combined with Fe₂O₃The mass ratio of (1): (0.33-2).

In the FeO (OH) @ MBC, the mass ratio of MBC to FeO (OH) is 1: (0.33-2).

Example 2:

this example is a specific application of the technical solution provided in example 1, and focuses on the preparation of various self-derived N-doped biochar MBCs obtained at different pyrolysis temperatures, which are further prepared into Fe₂O₃The @ MBC or FeO (OH) @ MBC composite material is prepared by respectively measuring the performance and parameter changes (degradation time, degradation rate, maximum degradation rate, change trend and the like) of various materials on catalyzing, activating PDS, adsorbing and degrading TPhP。

Example 2-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, the Fe prepared by adopting the biochar pyrolyzed at 350 ℃ twice and the inorganic mineral addition ratio (the mass ratio of the biochar to the inorganic mineral) of 1:2, the ball milling ratio of 1:100, the ball milling modification rotation speed of 500r/min and the ball milling modification duration of 12h is selected₂O₃The degradability was measured using @ MBC and FeO (OH) @ MBC as activators.

Adding a certain amount of biochar prepared at a secondary pyrolysis temperature of 350 ℃, inorganic mineral (Fe) and a certain amount of biochar into a TPhP sample solution with a measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the cumulative time of ball milling is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.5 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 3, and the degradation rate of the composite material for TPhP is 30.17% -31.14%.

Example 2-B:

in addition to the preparation method and preparation conditions of the composite material described in example 2-A, the composite material prepared by replacing the biochar secondarily pyrolyzed at 350 ℃ with the biochar secondarily pyrolyzed at 500 ℃ was used as an activator, and other degradation conditions were not changed. The result of the composite material determination is shown in fig. 4, and the degradation rate of the composite material to TPhP is 60.31% -69.86%.

Example 2-C:

in addition to the preparation method and preparation conditions of the composite material described in example 2-A, the composite material prepared by replacing the biochar secondarily pyrolyzed at 350 ℃ with the biochar secondarily pyrolyzed at 650 ℃ was used as an activator, and other degradation conditions were not changed. The result of the composite material determination is shown in fig. 5, and the degradation rate of the composite material to TPhP is 70.12% -75.51%.

Example 2-D:

based on the preparation method and preparation conditions of the composite material described in example 2-A, the composite material prepared by replacing the biochar pyrolyzed twice at 350 ℃ with the biochar pyrolyzed twice at 800 ℃ was used as an activator, and other degradation conditions were not changed. The result of the composite material determination is shown in fig. 6, and the degradation rate of the composite material to TPhP is 78.22% -79.30%.

Analysis of the data obtained in this example shows that when the TPhP concentration is 3.26 mg/L and the PDS concentration is 10mmol/L, Fe is added along with the increase of the secondary pyrolysis temperature in the charcoal preparation process₂O₃The composite material composed of @ MBC and FeO (OH) @ MBC has an increased degradation rate of TPhP. The optimal secondary pyrolysis preparation temperature of the biochar is 800 ℃, and Fe prepared under the condition₂O₃The maximum degradation rate of @ MBC and FeO (OH) @ MBC on TPhP is 79.30%.

Example 3:

this example is a specific application of the technical solution provided in example 1, and focuses on separately preparing various Fe under different ball milling modification rotation speeds₂O₃The material is a composite material of @ MBC or FeO (OH) @ MBC, and the performance and parameter changes (degradation time, degradation rate, maximum degradation rate, change trend and the like) of various materials for catalyzing, activating PDS, adsorbing and degrading TPhP are respectively measured.

Example 3-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, Fe prepared by adopting a biochar and inorganic mineral addition ratio (the mass ratio of biochar to inorganic mineral) of secondary pyrolysis at 800 ℃ of 1:2, a ball milling ratio of 1:100, a ball milling modification rotation speed of 350r/min and a ball milling modification duration of 12h is selected₂O₃The degradability was measured with @ MBC or FeO (OH) @ MBC as an activator.

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 350r/min, and the cumulative time of ball milling is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.5 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 7, and the degradation rate of the composite material for TPhP is 52.66% -58.67%.

Example 3-B:

fe prepared at a ball mill rotation speed of 500r/min based on the composite material preparation method and preparation conditions described in example 3-A₂O₃The @ MBC and FeO (OH) @ MBC composite material replaces the composite material prepared at 350r/min to be used as an activating agent, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 8, and the degradation rate of the composite material to TPhP is 66.16% -66.80%.

Example 3-C:

fe prepared at 650r/min rotation speed of ball mill based on the composite material preparation method and preparation conditions described in example 3-A₂O₃The @ MBC and FeO (OH) @ MBC composite material replaces the composite material prepared at 350r/min to be used as an activating agent, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 9, and the degradation rate of the composite material to TPhP is 60.91% -64.11%.

By analyzing the data obtained in this example, it can be seen that when the TPhP concentration is 3.26 mg/L, the PDS concentration is 10mmol/L, and Fe₂O₃When the ball milling modification rotating speed of @ MBC and FeO (OH) @ MBC is more than or equal to 500r/min, the degradation rate is more than 60 percent. The best choice is Fe in view of overall cost control in material preparation₂O₃The ball milling modification preparation speed of @ MBC and FeO (OH) @ MBC is 500r/min, and the maximum degradation rate is 66.80 percent.

Example 4:

this example is a specific application of the technical solution provided in example 1, and focuses on separately preparing various Fe types under different ball milling modification duration conditions₂O₃The material is a composite material of @ MBC or FeO (OH) @ MBC, and the performance and parameter changes of the materials on catalyzing, activating PDS, adsorbing and degrading TPhP are respectively measured.

Example 4-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, Fe prepared by adopting a biochar and inorganic mineral addition ratio (the mass ratio of biochar to inorganic mineral) of secondary pyrolysis at 800 ℃ of 1:2, a ball milling ratio of 1:100, a ball milling modification rotation speed of 500r/min and ball milling modification duration time totaling 4h is selected₂O₃The degradability was measured with @ MBC or FeO (OH) @ MBC as an activator.

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 4 hours₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.5 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 10, and the degradation rate of the composite material for TPhP is 58.76% -59.38%.

Example 4-B:

based on the preparation method and preparation conditions of the composite material described in example 4-A, Fe prepared with a ball milling duration of 4 hours was replaced with 6 hours in total₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 11, and the degradation rate of the composite material to TPhP is 62.55% -67.21%.

Example 4-C:

based on the preparation method and preparation conditions of the composite material described in example 4-A, Fe prepared with a ball milling duration of 4h was replaced with 12h as a cumulative total₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 12, and the degradation rate of the composite material to TPhP is 72.97% -76.79%.

Analysis of the data obtained above in this example revealed that when the TPhP concentration was 3.26 mg/L, the PDS concentration was10mmol/L, and Fe is added along with the duration of ball milling at the rotating speed of 500r/min₂O₃The binding performance of @ MBC or FeO (OH) @ MBC is improved, and the degradation rate of TPhP is increased. The best choice is Fe₂O₃The duration of the @ MBC or FeO (OH) @ MBC ball milling is 12h, and the maximum degradation rate is 76.79%.

Example 5:

this example is a specific application of the technical solution provided in example 1, and focuses on separately preparing a plurality of Fe types under different ball milling ratios₂O₃The material is a composite material of @ MBC or FeO (OH) @ MBC, and the performance and parameter changes of the materials on catalyzing, activating PDS, adsorbing and degrading TPhP are respectively measured.

Example 5-A:

based on the preparation method and preparation conditions of the composite material described in example 1, Fe prepared by using biochar pyrolyzed at 800 ℃ twice and inorganic mineral addition ratio (the mass ratio of biochar to inorganic mineral) of 1:2, ball milling modification rotation speed of 500r/min, ball milling modification duration time of 12 hours cumulatively, ball milling ratio of 1:10 (i.e., (biochar + inorganic mineral composite): grinding ball mass ratio =1: 10) was selected₂O₃The degradability was measured with @ MBC or FeO (OH) @ MBC as an activator.

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:10 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.5 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 13, and the degradation rate of the composite material for TPhP is 63.48% -77.59%.

Example 5-B:

based on the preparation method and preparation conditions of the composite material described in example 5-A, a ball milling ratio of 1:50 was used insteadFe prepared by ball milling in a ratio of 1:10₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material measurement is shown in fig. 14, and the degradation rate of the composite material to TPhP is 71.63% -71.91%.

Example 5-C:

based on the preparation method and preparation conditions of the composite material described in example 5-A, Fe prepared in a ball milling ratio of 1:100 was used instead of Fe prepared in a ball milling ratio of 1:10₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 15, and the degradation rate of the composite material to TPhP is 72.97% -76.79%.

By analyzing the above measured data in this example, when TPhP concentration is 3.26 mg/L and PDS concentration is 10mmol/L, Fe is increased with increasing ball milling ratio₂O₃The performance of @ MBC or FeO (OH) @ MBC is improved, and the degradation rate of TPhP is increased. The best choice is Fe₂O₃The ball milling ratio of @ MBC or FeO (OH) @ MBC is 1:100, and the maximum degradation rate is 76.79%.

Example 6:

this example is a specific application of the technical solution provided in example 1, and focuses on obtaining various Fe under the conditions of preparing biochar and inorganic mineral with different addition ratios₂O₃The material is a composite material of @ MBC or FeO (OH) @ MBC, and the performance and parameter changes of the materials on catalyzing, activating PDS, adsorbing and degrading TPhP are respectively measured.

Example 6-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, the addition ratio (mass ratio of biochar to inorganic mineral) of biochar and inorganic mineral subjected to secondary pyrolysis at 800 ℃ is 1:2, the ball milling modification speed is 500r/min, the ball milling modification duration is accumulated for 12 hours, the ball milling ratio is 1:100, and the prepared Fe₂O₃The degradability was measured with @ MBC or FeO (OH) @ MBC as an activator.

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, biochar and TPhP sample solution with the determination concentration of 3.26 mg/LOrganic mineral (Fe)₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.5 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 16, and the degradation rate of the composite material for TPhP is 78.22% -79.30%.

Example 6-B:

biochar, its mixture, and an inorganic mineral (Fe) were used in addition to the method and conditions for producing the composite material described in example 6-A₂O₃FeO (OH) was added in a mass ratio of 1:1 instead of Fe prepared in a 1:2 ratio₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 17, and the degradation rate of the composite material to TPhP is 72.97% -76.79%.

Example 6-C:

biochar, its mixture, and an inorganic mineral (Fe) were used in addition to the method and conditions for producing the composite material described in example 6-A₂O₃FeO (OH) was added in a mass ratio of 2:1 instead of Fe prepared in a 1:2 ratio₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 18, and the degradation rate of the composite material to TPhP is 76.83% -76.64%.

Example 6-D:

biochar, its mixture, and an inorganic mineral (Fe) were used in addition to the method and conditions for producing the composite material described in example 6-A₂O₃FeO (OH) was added in a mass ratio of 3:1 instead of Fe prepared in a 1:2 ratio₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 19, and the degradation rate of the composite material to TPhP is 71.88% -75.68%.

By applying the above to the present embodimentAnalysis of the measured data shows that the concentration of TPhP is 3.26 mg/L, the concentration of PDS is 10mmol/L, and Fe is added with the addition ratio of inorganic minerals₂O₃The performance of @ MBC or FeO (OH) @ MBC is improved, and the degradation rate of TPhP is increased. The best selection is Fe prepared when the addition ratio of the biochar to the inorganic mineral is 1:2₂O₃The degradation efficiency of @ MBC or FeO (OH) @ MBC on TPhP is the maximum, and the maximum degradation rate is 79.30%.

In other embodiments, the Fe₂O₃In @ MBC, MBC is combined with Fe₂O₃The mass ratio of (a) to (b) may also be 1: 0.33 or 1: 0.5, etc., in the range of 1: (0.33-2) can achieve the technical effect of the invention;

the same is true. In other embodiments, the mass ratio of MBC to feo (oh) in feo (oh) @ MBC may be 1: (0.33-2).

Example 7:

this example is a specific application of the technical solution provided in example 1, and focuses on different Fe₂O₃In the case where the amount of the composite material of @ MBC or FeO (OH) @ MBC was added, the change in the degradation rate of adsorbing and degrading TPhP in the case of catalyzing and activating PDS was measured.

Example 7-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, the addition ratio (mass ratio of biochar to inorganic mineral) of biochar and inorganic mineral subjected to secondary pyrolysis at 800 ℃ is 1:2, the ball milling modification speed is 500r/min, the ball milling modification duration is accumulated for 12 hours, the ball milling ratio is 1:100, and the prepared Fe₂O₃The degradation performance was measured by changing the amount of @ MBC or FeO (OH) @ MBC as an activator (concentration after addition).

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 0.05 g/L, the adding concentration of PDS is 10mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 20, and the degradation rate of the composite material for TPhP is 76.74% -76.99%.

Example 7-B:

in addition to the method and conditions for producing the composite material described in example 7-A, Fe was added in a concentration of 0.10 g/L₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 21, and the degradation rate of the composite material to TPhP is 86.00% -87.87%.

Example 7-C:

in addition to the method and conditions for producing the composite material described in example 7-A, Fe was added in a concentration of 0.25g/L₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material measurement is shown in fig. 22, and the degradation rate of the composite material to TPhP is 81.48% -82.84%.

Example 7-D:

in addition to the method and conditions for producing the composite material described in example 7-A, Fe was added in a concentration of 0.50g/L₂O₃The material of the @ MBC or FeO (OH) @ MBC composite is used as an activator, and other degradation conditions are not changed. The result of the composite material determination is shown in fig. 23, and the degradation rate of the composite material to TPhP is 78.22% -79.30%.

Example 7-F:

in addition to the method and conditions for producing the composite material described in example 7-A, Fe was added to the composite material in a concentration of 1.00g/L₂O₃The material of the composite of @ MBC and FeO (OH) @ MBC is taken as an activator, and other degradation conditions are unchanged. The result of the composite material determination is shown in fig. 24, and the degradation rate of the composite material to TPhP is 69.74% -78.13%.

By analyzing the data measured in the embodiment of the present invention, when the TPhP concentration is 3.26 mg/L and the PDS concentration is 10mmol/L,Fe₂O₃when the dosage of @ MBC or FeO (OH) @ MBC is 0.10-0.25 g/L, the TPhP can be effectively degraded, and the degradation rate is more than 80 percent. Optimum selection of Fe₂O₃The dosage of @ MBC and FeO (OH) @ MBC is 0.10 g/L, and the maximum degradation rate is 87.87%.

Example 8:

this example is a specific application of the technical solution provided in example 1, and focuses on the study of determining the degradation rate change of the composite material for catalyzing, activating PDS, adsorbing, and degrading TPhP under different PDS dosage (concentration).

Example 8-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, the addition ratio (mass ratio of biochar to inorganic mineral) of biochar and inorganic mineral subjected to secondary pyrolysis at 800 ℃ is 1:2, the ball milling modification speed is 500r/min, the ball milling modification duration is accumulated for 12 hours, the ball milling ratio is 1:100, and the prepared Fe₂O₃The degradation performance was measured with respect to @ MBC or FeO (OH) @ MBC as an activator by changing the amount of PDS added (concentration after addition).

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 12h₂O₃The @ MBC and FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration is 1.00g/L, the adding concentration of PDS is 3 mmol/L, and the shaking reaction is carried out in a shaking table for 8 hours. The determination result is shown in fig. 25, and the degradation rate of the composite material for TPhP is 35.34% -43.48%.

Example 8-B:

based on the preparation method and preparation conditions of the composite material described in example 8-A, the concentration of the added PDS was 5 mmol/L, and other degradation conditions were unchanged. The result of the composite material determination is shown in fig. 26, and the degradation rate of the composite material to TPhP is 51.87% -52.87%.

Example 8-C:

based on the preparation method and preparation conditions of the composite material described in example 8-A, the concentration of the added PDS was 8 mmol/L, and other degradation conditions were unchanged. The result of the composite material determination is shown in fig. 26, and the degradation rate of the composite material to TPhP is 58.92% -62.31%.

Example 8-D:

based on the preparation method and preparation conditions of the composite material described in example 8-A, the concentration of the added PDS was 10mmol/L, and other degradation conditions were unchanged. The result of the composite material determination is shown in fig. 28, and the degradation rate of the composite material to TPhP is 86.00% -87.87%.

Example 8-E:

based on the preparation method and preparation conditions of the composite material described in example 8-A, the concentration of PDS added was 12mmol/L, and other degradation conditions were unchanged. The result of the composite material determination is shown in fig. 29, and the degradation rate of the composite material to TPhP is 72.38% -73.55%.

Analysis of the data obtained in this example shows that Fe is present at a TPhP concentration of 3.26 mg/L₂O₃The dosage of @ MBC or FeO (OH) @ MBC is 0.1 g/L, the degradation rate can be improved by increasing the concentration of PDS, and the peak value is 10mmol/L, when the concentration of PDS is 10-12 mmol/L, TPhP can be effectively degraded, and the degradation rate is more than 70%. The best selected PDS concentration is 10mmol/L, the maximum degradation rate is 87.87%.

Example 9:

the present example is a specific application of the technical solution provided in example 1, and focuses on the study of determining the degradation rate change of the composite material for catalyzing, activating PDS, adsorbing, and degrading TPhP under different pH values.

Example 9-A:

on the basis of the preparation method and preparation conditions of the composite material described in example 1, the addition ratio (mass ratio of biochar to inorganic mineral) of biochar and inorganic mineral subjected to secondary pyrolysis at 800 ℃ is 1:2, the ball milling modification speed is 500r/min, and the ball milling modification duration is longFe prepared by accumulating for 12h and ball milling ratio of 1:100₂O₃And the degradation performance is measured by changing the pH value of the water body by using the @ MBC or FeO (OH) @ MBC as an activating agent.

Adding a certain amount of biochar prepared at the secondary pyrolysis temperature of 800 ℃, and inorganic mineral (Fe) into TPhP sample solution with the measured concentration of 3.26 mg/L₂O₃FeO (OH) is added in a mass ratio of 1:2, the mass ratio of the composite material to the grinding balls is 1:100 during ball milling modification, the rotating speed of the ball mill is 500r/min, and the ball milling duration is 12h₂O₃The @ MBC or FeO (OH) @ MBC composite material is used as an activating agent, the adding concentration of the composite material is 0.10 g/L, and the adding concentration of PDS is 10 mmol/L; naturally adopting the pH initial value of water body to be 6.0-6.2, and oscillating and reacting in a shaking table for 8 h. The determination result is shown in fig. 30, and the degradation rate of the composite material for TPhP is 86.00% -87.87%.

Example 9-B:

in addition to the method and conditions for preparing the composite material described in example 9-A, the TPhP sample solution was adjusted to pH 3.0 without changing other degradation conditions. The result of the composite material determination is shown in fig. 31, and the degradation rate of the composite material to TPhP is 52.36% -59.37%.

Example 9-C:

in addition to the method and conditions for preparing the composite material described in example 9-A, the TPhP sample solution was adjusted to pH 5.0 without changing other degradation conditions. The result of the composite material measurement is shown in fig. 32, and the degradation rate of the composite material for TPhP is 66.11% -71.40%.

Example 9-D:

in addition to the method and conditions for preparing the composite material described in example 9-A, the TPhP sample solution was adjusted to pH 9.0 without changing other degradation conditions. The result of the composite material determination is shown in fig. 33, and the degradation rate of the composite material to TPhP is 70.26% -74.36%.

Example 9-E:

in addition to the method and conditions for preparing the composite material described in example 9-A, the TPhP sample solution was adjusted to pH 11.0 without changing other degradation conditions. The result of the composite material determination is shown in fig. 34, and the degradation rate of the composite material to TPhP is 45.93% -53.46%.

Analysis of the data obtained in this example shows that the complex material has a wide pH adaptation range, and when the pH is 6.0-9.0, no adjustment is required, and a high degradation rate can be achieved. The optimum selection is a pH value of 6.0-6.2 (initial value), no additional adjustment is needed, and the maximum degradation rate is 87.87%.

The method improves the effect of removing the TPhP pollutants in the water body, simultaneously contributes to reducing the total consumption and the sowing and application times of a material system (and avoids recycling by reducing the material cost), does not need to adjust the pH value, greatly reduces the sewage treatment cost, and is convenient for large-area popularization. Through practical tests, the TPhP in the water body can be removed through one-time sowing and application and 8-hour degradation, and the TPhP reaches a set standard; compared with the traditional technology, the overall water body treatment scheme of the invention can save the total cost by more than 70 percent and can improve the degradation efficiency by more than 30 percent.

It is to be noted that Fe provided by the present invention₂O₃@ MBC and FeO (OH) @ MBC may be fully equivalents. In other embodiments of the present invention, different schemes obtained by specifically selecting the steps, components, ratios and process parameters described in the present invention can achieve the technical effects described in the present invention, and therefore, the present invention does not list them one by one.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. All equivalent changes in the components, proportions and processes according to the present invention are intended to be covered by the scope of the present invention.

Claims

1. A method for degrading TPhP, comprising the steps of:

s1: preparing an N-doped biochar-inorganic mineral composite material, which comprises the following steps: fe₂O₃The material is one of @ MBC or FeO (OH) @ MBC, the TPhP is triphenyl phosphate, the MBC is self-derived N-doped charcoal, and the MBC is prepared by adopting the following steps:

washing poultry feather with ultrapure water, and drying in an oven at 60 ℃;

carrying out secondary pyrolysis by taking the primary pyrolysis biochar material as a raw material, heating the raw material to 350 ℃, 500 ℃, 650 ℃ and 800 ℃ at the room temperature of 10 ℃/min, keeping the temperature for 2h, and then cooling the raw material to 75 ℃ at the temperature of 10 ℃/min, so as to correspondingly prepare four kinds of self-derived N-doped biochar MBC with the pyrolysis conditions of 350 ℃, 500 ℃, 650 ℃ and 800 ℃;

the secondary pyrolysis increases the proportion of nitrogen in the biochar to be more than 10wt%, and more graphite nitrogen and pyridine nitrogen are generated;

the N-doped biochar-inorganic mineral composite material is ball-milled modified Fe₂O₃@ MBC or one of FeO (OH) @ MBC, and the MBC is mixed with Fe as an inorganic mineral₂O₃Or FeO (OH) powder is simultaneously placed in a ball milling tank for ball milling modification; in the process of preparing the biochar-inorganic mineral by ball milling, the original carbon skeleton structure of the biochar is broken, so that the particle size of the biochar is reduced and the biochar is in an irregular flaky fragment structure, the surface of the fragment structure is rough, and more active sites are exposed in the process of catalytically degrading TPhP;

s3: adding PDS into the sewage water body, adjusting the concentration of the PDS to a preset value, and adding an N-doped biochar-inorganic mineral complexStirring or oscillating for 4-8 h to enable the N-doped biochar-inorganic mineral composite material to catalyze and activate PDS, wherein the N-doped biochar-inorganic mineral composite material is used as an adsorbent and an activator, and inorganic mineral Fe₂O₃Or FeO (OH) is bonded on the surface of the biochar fragment structure through Fe-O and Fe-OH chemical bonds and passes through Fe in the catalytic reaction process²⁺/Fe³ ⁺Catalyzing persulfate to generate hydroxyl free radicals and sulfate free radicals with strong oxidizing property, adsorbing and degrading TPhP in a water body, and providing a nitrogen source for the degradation reaction process by using self-derived N-doped biochar; the active site improves the electron transfer rate and promotes PDS activation and pollutant degradation;

2. The method for degrading TPhP according to claim 1, wherein the TPhP is a TPhP,

the step S3 further includes: when the initial pH value of the water body is 6-9, adjustment is not needed.

3. The method for degrading TPhP according to claim 1, wherein the TPhP is a TPhP,

the adding amount of the N-doped biochar-inorganic mineral composite material in the step S3 is 0.1-0.25 g/L.

4. The method for degrading TPhP according to claim 1, wherein the TPhP is a TPhP,

the concentration preset value of PDS in the step S3 is 10-12 mmol/L.

5. The method for degrading TPhP according to claim 1, wherein the TPhP is a TPhP,

in the FeO (OH) @ MBC, the mass ratio of MBC to FeO (OH) is 1: (0.33-2).

6. An N-doped biochar-inorganic mineral composite material for implementing the TPhP degradation method of any one of claims 1 to 5, characterized in that the material is Fe modified by ball milling₂O₃@ MBC or one of FeO (OH) @ MBC, wherein MBC is self-derived N-doped charcoal, and the MBC and Fe are mixed₂O₃Or FeO (OH) powder is simultaneously placed in a ball milling tank for ball milling modification.

7. A method for preparing the N-doped biochar-inorganic mineral composite material according to claim 6, which comprises the following steps:

m1: preparing MBC:

washing poultry feather with ultrapure water, and drying in an oven at 60 ℃;

m2: preparing an N-doped biochar-inorganic mineral composite material:

separately prepared from hematite Fe₂O₃Or an inorganic mineral formed from goethite FeO (OH) powder;

weighing any one of the self-derived N-doped biochar MBC and the inorganic mineral Fe in sequence according to a set mass ratio₂O₃Or one of FeO (OH) powder is ball-milled and modified, and MBC and Fe are mixed₂O₃Or one of FeO (OH) powder is simultaneously placed in a ball milling tank, clockwise rotation is carried out for 2h at one of the rotation speeds of 350r/min, 500r/min and 650r/min respectively, then operation is stopped for 30 min, and anticlockwise rotation is carried out for 2h at the same rotation speed; will stop running clockwise and clockwise respectivelyThe anticlockwise rotation process is repeatedly and alternately operated for a plurality of times, so that the time accumulation of ball milling rotation reaches 4h, 6h and 12h respectively, and Fe is ensured₂O₃Or goethite FeO (OH) powder is combined with MBC respectively and is used for MBC and Fe₂O₃Or simultaneously modifying goethite FeO (OH), namely respectively preparing a plurality of N-doped biochar-inorganic mineral composite materials under different preparation conditions.

8. The production method according to claim 7,

9. The production method according to claim 7,

in the step M2, the mass ratio of the MBC to the inorganic mineral is respectively as follows: 1:2, 1:1, 2:1 and 3: 1.

10. The production method according to claim 7,