CN114682276B - Method for preparing transition metal phosphide/biochar material by using rice bran - Google Patents

Method for preparing transition metal phosphide/biochar material by using rice bran Download PDF

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CN114682276B
CN114682276B CN202011604952.6A CN202011604952A CN114682276B CN 114682276 B CN114682276 B CN 114682276B CN 202011604952 A CN202011604952 A CN 202011604952A CN 114682276 B CN114682276 B CN 114682276B
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transition metal
rice bran
phosphide
biochar
metal phosphide
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CN114682276A (en
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王雅博
何志梅
张永奎
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Sichuan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/36—Organic compounds containing halogen

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Abstract

The invention discloses a method for preparing transition metal phosphide/biochar materials by utilizing rice bran, which comprises the following steps: grinding testa oryzae with ferric chloride hexahydrate and 1-9 times of sodium chloride and potassium chloride mixed salt in ball mill for 2-5 h times to obtain 500-1000 times mixture o Calcining under the protective atmosphere of C to obtain the iron phosphide/biological carbon material. The material can be used as an adsorbent and a catalyst to adsorb fluoroquinolone antibiotics in water, and can catalyze and activate potassium hydrogen peroxymonosulfate composite salt to effectively degrade the fluoroquinolone antibiotics. The invention provides a simple and green preparation method of transition metal phosphide, and the phosphorus resource in biomass is reused, and meanwhile, the fluoroquinolone antibiotics in the water body are efficiently removed.

Description

Method for preparing transition metal phosphide/biochar material by using rice bran
Technical Field
The invention belongs to the field of transition metal phosphide and carbon materials, and particularly relates to a method for preparing a transition metal phosphide/biological carbon material by using rice bran.
Background
The transition metal phosphide is a generic name of binary or multi-component compounds formed by transition metal atoms and phosphorus atoms, and has the advantages of excellent thermal stability, excellent chemical stability, high hardness, high strength and good heat conduction and electric conduction performances. The traditional synthesis of transition metal phosphide often uses highly toxic organic phosphorus as a phosphorus source precursor, or requires complex reduction process conditions, and the application of the transition metal phosphide is limited by high cost and environmental pressure in the preparation process. In recent years, a method for preparing transition metal phosphide by taking inherent phosphorus element in biomass as phosphorus source has attracted attention due to the characteristics of sustainable green, simple preparation and environmental friendliness. The phosphorus content in rice bran is about 1.34%, and the rice bran is huge in quantity and green and renewable, wherein phosphorus resources are not ignored. The transition metal phosphide prepared by taking rice bran as a phosphorus source can solve the cost and environmental problems in the traditional preparation process.
The basic principle of the advanced oxidation technology is that oxidant is activated in solution to generate free radical with strong oxidability by using technical means such as high temperature and high pressure, electricity, ultrasound, light irradiation, catalyst and the like, and the free radical acts on organic matters to thoroughly oxidize and decompose the organic matters. Transition metal phosphides can act as catalysts for advanced oxidation techniques due to their good electron transfer properties. But part of the transition metal phosphide leaches out of the metal ions (Co 2+ 、Ni 2+ Etc.) can cause secondary pollution to the water body and is difficult to recycle. The transition metal phosphide/biochar composite material prepared by taking biomass as a precursor can effectively relieve leaching of metal ions and agglomeration of active centers. Therefore, the invention selects rice bran as a typical agricultural product processing byproduct as a raw material, prepares the transition metal phosphide/biochar composite material through simple ball milling treatment, high Wen Queyang pyrolysis and other processes, not only finds a safe and green phosphorus source, but also provides a new idea of recycling low-value biomass generated in the process of processing a large number of huge agricultural products, and simultaneously provides a new way for removing fluoroquinolone pollutants in water.
Disclosure of Invention
The invention aims to provide a method for preparing transition metal phosphide/biochar materials by using rice bran, which can be used for catalytically activating potassium hydrogen peroxymonosulfate composite salt (degrading environmental organic pollutants, solving the problems of high cost and high toxicity encountered by the traditional chemical method for preparing transition metal phosphide and simultaneously realizing the removal of fluoroquinolone organic pollutants in water, and the invention is realized by the following technical scheme.
A method for preparing transition metal phosphide/biochar material by using rice bran comprises the following specific operations:
(1) Weighing 2 g rice bran, 0.096-0.869 g ferric trichloride hexahydrate, 2-18 g sodium chloride and 2-18 g potassium chloride, placing the rice bran in an agate grinding tank, placing a plurality of agate grinding medium balls in the agate grinding tank, and grinding 3 h at 300 rpm to obtain precursor mixed powder;
(2) Transferring the mixed powder obtained in the step (1) into a corundum crucible, placing the corundum crucible into a tube furnace, calcining under an inert atmosphere, heating at a speed of 5 ℃/min, calcining at a temperature of 900 ℃ for 2 h, and naturally cooling to room temperature to obtain a solid mixture material;
(3) Washing the mixture material obtained in the step (2) with deionized water, removing sodium chloride and potassium chloride, and drying in a 60 ℃ oven to obtain an iron phosphide/biochar composite material;
(4) Preparing 10 mg/L of levofloxacin solution, taking the iron phosphide/biochar composite material obtained in the step (3) as an adsorbent and a catalyst under the condition of stirring at room temperature, taking potassium hydrogen peroxymonosulfate composite salt as an oxidant, adding the potassium hydrogen peroxymonosulfate composite salt into the levofloxacin solution, and sampling and detecting the concentration of the levofloxacin in the solution at regular time.
The product is shown as Fe by X-ray crystal diffraction analysis 2 P。
Optionally, in step (1), the transition metal used is selected from iron, cobalt, copper.
Optionally, in step (2), the protective atmosphere used for the mixture is nitrogen or argon.
Optionally, in step (4), the iron phosphide/biochar composite material is used in an amount of 0.1-0.4 g/L, the potassium hydrogen peroxymonosulfate composite salt is used in an amount of 0.1-0.4 g/L, the reaction temperature is 25 ℃, and the reaction stirring rate is 600 rpm.
The innovation and beneficial effects of the invention are as follows: (1) According to the invention, rice bran is used as a phosphorus source and a carbon source for the first time, and the iron phosphide/biological carbon material with adsorptivity and catalytic activity is prepared through two steps of solid ball milling and high Wen Queyang pyrolysis, so that organic pollutants are removed by adsorbing and catalyzing potassium hydrogen peroxymonosulfate composite salt, the reutilization of phosphorus and carbon resources in biomass is realized, and meanwhile, the preparation method of the transition metal phosphide is provided. (2) The iron phosphide/biochar material prepared by the method has certain adsorption performance, good catalytic activity and dual functions, and achieves the purpose of efficiently removing fluoroquinolone pollutants in water.
Description of the drawings:
FIG. 1 is an X-ray crystallography chart of an iron phosphide/biochar composite material prepared in example 1 of the present invention; FIG. 2 is a graph showing the effect of removing levofloxacin from various materials obtained in example 2 of the present invention.
Detailed Description
For a better understanding of the present invention, the present invention will be described in further detail with reference to the following examples and drawings; it should be specifically noted that the examples are only for further illustrating the present invention, and the scope of the present invention is not limited thereto.
Embodiment case 1: the rice bran as raw material 2 g, ferric trichloride hexahydrate 0.096-0.869 g, sodium chloride 2-18 g and potassium chloride 2-18 g are placed in an agate grinding pot, a plurality of agate grinding medium balls are placed in the agate grinding pot, and grinding is carried out at 300 rpm for 3 h. Transferring the obtained mixed powder into a corundum crucible, calcining in a protective atmosphere in a tube furnace at a heating rate of 5 ℃/min, a calcining temperature of 900 ℃ and a calcining time of 2 h, and cooling to obtain a solid mixture material. Thoroughly washing the obtained mixture material with deionized water to remove sodium chloride and potassium chloride, and drying in a 60 ℃ oven to obtain an iron phosphide/biochar composite material which is named asFe 2 P/BC. To study the influence of iron ions and salts on the adsorption and catalytic performance of the material, the same preparation method is adopted to obtain a sample without ferric trichloride hexahydrate and a sample without sodium chloride and potassium chloride respectively, and the samples are namedBCA kind of electronic device with high-pressure air-conditioning systemFe 2 P/BC free . The X-ray crystallography analysis of the samples is shown in figure 1.
Embodiment case 2: raw material 2 gRice bran, 0.096-0.869 g ferric trichloride hexahydrate, 2-18 g sodium chloride, 2-18 g potassium chloride are placed in an agate grinding pot, a plurality of agate grinding medium balls are placed in the agate grinding pot, and 3 h is ground at 300 rpm. Transferring the obtained mixed powder into a corundum crucible, and calcining in a protective atmosphere in a tube furnace at a heating rate of 5 ℃/min, a calcining temperature of 900 ℃ and a calcining time of 2 h to obtain a solid mixture material. Thoroughly washing the obtained mixture material with deionized water to remove sodium chloride and potassium chloride, and drying in a 60 ℃ oven to obtain an iron phosphide/biochar composite material which is named asFe 2 P/BC. To study the influence of iron ions and salts on the catalytic performance of the material, the same preparation method is adopted to obtain a sample without ferric trichloride hexahydrate and a sample without sodium chloride and potassium chloride respectively, and the samples are namedBCA kind of electronic device with high-pressure air-conditioning systemFe 2 P/ BC free . In order to examine the adsorption and degradation properties of the iron phosphide/biochar material prepared by the method, the following experiment is carried out: preparing 10 mg/L of levofloxacin solution, stirring at room temperature and 600 rpm, adding 25 mg material into the levofloxacin solution, sampling at fixed time to determine the concentration of the residual levofloxacin in the system, and adding 10 mg potassium hydrogen Peroxymonosulfate (PMS) when the adsorption balance is reached, i.e. the concentration of the residual levofloxacin in the solution is unchanged, sampling at fixed time to determine the concentration of the residual levofloxacin in the system. The measurement result shows that under the system, during the adsorption process of 30 min, fe 2 P/BC、Fe 2 P/BC free And the adsorption removal rate of BC sample to levofloxacin is 29.77%, 2.01% and 24.46%, respectively, fe in the subsequent 30 min catalytic degradation process 2 P/BC、Fe 2 P/BC free And the final removal rate of BC sample to levofloxacin respectively reaches 96.60%, 56.80% and 42.99%, and the degradation rate constants are respectively 0.125 min -1 ，0.034 min -1 ，0.011 min -1 . The experimental comparison results are shown in figure 2.

Claims (4)

1. A method for preparing transition metal phosphide/biochar material by using rice bran, which is characterized by comprising the following steps:
(1) Weighing 2 g rice bran, 0.096-0.869 g ferric trichloride hexahydrate, 2-18 g sodium chloride and 2-18 g potassium chloride, placing the rice bran in an agate grinding tank, placing a plurality of agate grinding medium balls in the agate grinding tank, and grinding 3 h at 300 rpm to obtain precursor mixed powder;
(2) Transferring the mixed powder obtained in the step (1) into a corundum crucible, placing the corundum crucible into a tube furnace, calcining under an inert atmosphere, heating at a speed of 5 ℃/min, calcining at a temperature of 900 ℃ for 2 h, and naturally cooling to room temperature to obtain a solid mixture material;
(3) Washing the mixture material obtained in the step (2) with deionized water, removing sodium chloride and potassium chloride, and drying in a 60 ℃ oven to obtain an iron phosphide/biochar composite material;
(4) Preparing 10 mg/L of levofloxacin solution, taking the iron phosphide/biochar composite material obtained in the step (3) as an adsorbent and a catalyst under the condition of stirring at room temperature, taking potassium hydrogen peroxymonosulfate composite salt as an oxidant, adding the potassium hydrogen peroxymonosulfate composite salt into the levofloxacin solution, and sampling and detecting the concentration of the levofloxacin in the solution at regular time.
2. The method for preparing a transition metal phosphide/biochar material using rice bran as claimed in claim 1, wherein the transition metal is at least one selected from iron, cobalt and copper.
3. The method for preparing transition metal phosphide/biochar material using rice bran as claimed in claim 1, wherein the protective atmosphere used for calcination in step (2) is nitrogen or argon.
4. The method for preparing transition metal phosphide/biochar material using rice bran as claimed in claim 1, wherein the amount of iron phosphide/biochar material used in step (4) is 0.1-0.4 g/L, the amount of potassium hydrogen peroxymonosulfate complex salt is 0.1-0.4 g/L, the reaction temperature is 25 ℃, and the reaction stirring rate is 600 rpm.
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CN115448257B (en) * 2022-09-15 2023-07-14 浙江金科日化新材料股份有限公司 Potassium hydrogen peroxymonosulfate compound salt spherulites and preparation method thereof

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CN109772385A (en) * 2019-02-25 2019-05-21 浙江工业大学 A kind of metal phosphide catalyst and its preparation method and application that carbon is self-supported
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CN111434607A (en) * 2019-01-11 2020-07-21 国家纳米科学中心 Metal phosphide and heteroatom-doped porous carbon composite material and preparation and application thereof
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