CN111013541A - Preparation and use method of modified waste argil charcoal for removing endocrine disruptors and antibiotics in water - Google Patents

Preparation and use method of modified waste argil charcoal for removing endocrine disruptors and antibiotics in water Download PDF

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Publication number
CN111013541A
CN111013541A CN202010008700.0A CN202010008700A CN111013541A CN 111013541 A CN111013541 A CN 111013541A CN 202010008700 A CN202010008700 A CN 202010008700A CN 111013541 A CN111013541 A CN 111013541A
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carbon
waste
antibiotics
modified
water
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CN202010008700.0A
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Chinese (zh)
Inventor
万东锦
陈静
陈瑶
史亚慧
张健
张良波
李进松
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Henan University of Technology
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Henan University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen

Abstract

The invention relates to a preparation and application method of modified spent bleaching clay carbon for removing endocrine disruptors and antibiotics in water, belonging to the application field of water treatment technology. Endocrine disruptors and antibiotics are common organic pollutants in water, are complex in type, are not easy to degrade and are easy to cause persistent water environment pollution. The modified waste argil carbon prepared by the method has the advantages of high specific surface area and developed pore structure, can quickly and efficiently remove endocrine disruptors and antibiotics in water, and can quickly perform solid-liquid separation by decompression suction filtration, filtration or centrifugation. The material can be regenerated by a simple method after inactivation, and has the potential of multiple applications. The raw material in the technology is the waste argil, the source is wide, the price is low, the environment is protected, the regeneration technology is simple, and the purpose of treating wastes with processes of wastes against one another can be achieved.

Description

Preparation and use method of modified waste argil charcoal for removing endocrine disruptors and antibiotics in water
The technical field is as follows:
the invention provides a preparation and application method of modified spent bleaching clay carbon for removing endocrine disruptors and antibiotics in water, belonging to the application field of water treatment technology. The modified spent bleaching clay carbon prepared by the method can be regenerated by a simple method after being inactivated, has the potential of multiple applications, and can effectively remove endocrine disruptors and antibiotics in water due to the specific physical and chemical properties and abundant pore structures of the modified spent bleaching clay carbon.
Background art:
endocrine Disrupting Compounds (EDCs) are an organic pollutant, over 87000 known chemicals, including natural and synthetic hormones and their degradation products, as well as a variety of compounds with hormonal activity from a variety of different applications, can interfere with the endocrine or hormonal system and are often found in aquatic environments around the world, having acute toxicity to aquatic organisms, even at very low concentrations (1 mg/m)3) It also produces estrogenic effects in humans, which can lead to sexual dysfunction, deformity, and immune system disorders. Therefore, it is of paramount importance to remove the EDCs from the body of water in order to make efficient use of water resources.
Antibiotics are widely used in the treatment of bacterial infections and in feed additives for promoting animal growth in aquaculture, and also as veterinary drugs in animal husbandry. However, antibiotics are not completely absorbed and metabolized in the human or animal body, and are mostly released into the environment through urine and feces, so that they are ubiquitous in the aqueous environment. The antibiotics have stable structural property and poor biodegradability, and human beings or animals eat food or water containing antibiotic residues for a long time to enable organisms to generate drug-resistant bacteria, so that organ diseases and the like are caused. Therefore, it is necessary to remove antibiotics from water to reduce the pollution of water environment.
Research on the removal of EDCs and antibiotics from water bodies has mainly involved chemical, biological and physical methods. The chemical and biological methods mainly comprise advanced oxidation, ozonolysis and a membrane bioreactor, but have the defects of high cost, low treatment efficiency, long running period, difficult operation and the like. In comparison, adsorption is an important physical-chemical method in water treatment, has low cost, simple process and operation, economy and high efficiency, avoids the risk of generation of high-toxicity metabolites, and is considered to be one of the most promising and effective methods for removing the EDCs and antibiotics in the water treatment technology. Currently, among the various types of adsorbents, mainly based on zeolites, clay/minerals, chitosan, agricultural wastes, carbon and nano/composite materials, carbonaceous materials are the most widely studied and applied water purification adsorbents.
Activated clays, also known as fullers' earth, are used in the edible oil refining industry. The refined bleaching earth is called waste clay. The waste clay mainly comprises grease which generally contains 20-40% of grease and SiO2、Al2O3And the like. The waste argil is used as a byproduct of oil processing, and is troubled by the treatment problem of the waste argil in all countries in the world. Therefore, with the popularization of the concept of efficient resource recycling and the rapid development of scientific technology, the waste argil generated in the grease industry is recycled and comprehensively utilized, so that the environment is protected, the reasonable utilization of resources is promoted, and considerable economic benefits can be brought to enterprises.
The waste clay carbon is generated by high-temperature pyrolysis and carbonization of waste clay under an oxygen-free condition, can be used as an adsorbent, has the defects of small specific surface area, undeveloped pore structure and the like, and is not beneficial to adsorbing pollutants. In order to improve the adsorption performance of the spent bleaching clay carbon, the spent bleaching clay carbon needs to be modified to obtain an ideal material structure. Therefore, the research is focused on finding a scientific and effective method for preparing the modified spent bleaching earth carbon material capable of efficiently adsorbing the EDCs and the antibiotics.
The preparation and use method of the hydrofluoric acid (HF) modified waste argil carbon for removing endocrine disruptors and antibiotics in water, which is provided by the invention, can effectively remove the endocrine disruptors and the antibiotics in water and meet the environmental protection trend of treating wastes with processes of wastes against one another, and the technology is not reported in the technical field of water treatment at present.
The invention content is as follows:
the invention aims to provide a reproducible adsorption material with high efficiency aiming at endocrine disruptors and antibiotic pollutants in water. The modified spent bleaching clay carbon has a high specific surface area and a rich pore structure, so that endocrine disruptors and antibiotics in water can be effectively removed.
The invention relates to a preparation method of an adsorption material for removing endocrine disruptors and antibiotics in water, which comprises the following steps: the method comprises the steps of drying the waste argil, pyrolyzing the dried waste argil in an oxygen-free atmosphere to obtain waste argil carbon, and modifying the waste argil carbon by using hydrofluoric acid to obtain a material with high adsorption capacity.
The invention relates to a using method of an adsorbing material for removing endocrine disruptors and antibiotics in water, which comprises the following steps: and (3) removing endocrine disruptors and antibiotics in water by utilizing modified spent bleaching clay carbon adsorption. After adsorption, the solid-liquid separation is rapidly finished by a method of decompression suction filtration, filtration or centrifugation, so that the water body polluted by endocrine disrupters and antibiotics is purified.
The invention relates to a regeneration method of an adsorption material for removing endocrine disruptors and antibiotics in water, which comprises the following steps: and soaking the modified waste clay carbon without the adsorption activity by adopting alkali liquor to obtain regenerated modified waste clay carbon.
The adsorbing material prepared by the method of anaerobic pyrolysis and hydrofluoric acid modification can be used for removing endocrine disruptors and antibiotic pollutants in water. In order to achieve the above object, the present invention adopts the following technical solutions.
The waste argil carbon is prepared by the following technical scheme:
(1) drying the waste argil for 6-72 hours at the temperature of 40-105 ℃;
(2) controlling the particle size to be less than 5.0 mm by grinding or crushing;
(3) and (3) putting the waste clay particles in an oxygen-free atmosphere with a closed system or under the protection of inert gas (nitrogen or argon) and pyrolyzing for 0.5-4 h at 300-1200 ℃, and taking out when the temperature is lower than 100 ℃ to obtain the waste clay carbon.
The modified waste clay carbon is prepared by the following technical scheme:
(1) drying the waste argil carbon for 6-72 hours at the temperature of 40-150 ℃;
(2) controlling the particle size to be less than 5.0 mm by grinding or crushing;
(3) placing the waste argil carbon and hydrofluoric acid after fully mixing for 3-72 h, wherein the mass of the waste argil carbon is as follows: the volume of hydrofluoric acid is =1g:5 mL-1 g:50 mL;
(4) carrying out solid-liquid separation on the waste argil carbon and hydrofluoric acid, and washing the rest solid;
(5) drying the washed solid for 6-72 h at the temperature of 40-150 ℃;
(6) and (3) grinding or crushing the dried solid to control the particle size to be less than 5.0 mm, thus obtaining the modified waste argil carbon.
The use method of the modified spent bleaching clay charcoal for removing endocrine disruptors and antibiotics comprises the following steps:
adding modified waste argil carbon to a water body to be purified, which is polluted by endocrine disruptors and/or antibiotics, wherein the adding amount is 0.01-25 g/L, fully and uniformly mixing, enabling the adsorption time to last for 0.5-24 h, and performing vacuum filtration or filtration after adsorption is completed to realize solid-liquid separation.
The inactivated modified spent bleaching clay carbon is regenerated by an alkali liquor soaking method:
(1) drying the modified waste argil carbon without the adsorption activity for 6-72 hours at the temperature of 40-150 ℃;
(2) soaking the dried modified waste argil carbon by using an alkali solution for 6-72 hours, wherein the alkali solution can be any one of sodium hydroxide and potassium hydroxide, and the concentration range of the alkali solution is 0.1-5 mol/L;
(3) carrying out solid-liquid separation and washing by a method of decompression suction filtration, filtration or centrifugation;
(4) and drying the washed modified waste clay carbon for 6-72 h at the temperature of 40-150 ℃ to obtain the regenerated modified waste clay carbon.
Compared with the prior art, the invention has the following outstanding advantages:
(1) the raw material of the carbon is the waste argil which is obtained from the refining process of the vegetable oil, has wide source and low price, is beneficial to protecting the environment and can achieve the aim of treating wastes with processes of wastes against one another.
(2) The method uses hydrofluoric acid to treat the waste carclazyte carbon, increases the specific surface area of the waste carclazyte carbon, enriches the pore structure of the waste carclazyte carbon, is beneficial to adsorbing and removing antibiotics which secrete interferents, and improves the adsorption capacity by about 5 times compared with unmodified waste carclazyte carbon and purchased commercial activated carbon.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described in detail with reference to specific examples, which should be understood as merely illustrative and not restrictive, and various equivalent modifications of the present invention, which fall within the scope of the appended claims, will be suggested to those skilled in the art after reading the present invention.
Example 1:
preparing waste clay carbon: and (3) drying the waste argil in an oven at 105 ℃ for 24 hours, and grinding the waste argil to a particle size of less than 0.15 mm by using a mortar. The screened spent bleaching earth particles were placed in a vacuum tube furnace and pyrolyzed for 2 h under nitrogen atmosphere (150 mL/min) at 700 ℃. And taking out the waste argil carbon after the temperature is reduced to 30 ℃.
Preparing modified waste clay carbon: weighing 10 g of waste argil carbon, fully mixing with 150 mL of hydrofluoric acid, standing for 36 h, carrying out solid-liquid separation by suction filtration, and washing the material with deionized water. And (3) drying the washed material in a 65 ℃ oven for 24h to obtain the modified waste argil carbon.
Application to removal of endocrine disruptors-bisphenol a: for an initial concentration of 50 mg/L of bisphenol A solution, 500ml of the solution was placed in a stoppered conical flask. Weighing 0.5 g of the adsorbing material, putting into a conical flask, continuously stirring by using a magnetic stirrer to uniformly mix the adsorbing material and the conical flask, carrying out mixing and adsorbing time of 6 hours at room temperature, carrying out solid-liquid separation by using reduced pressure suction filtration after adsorption is finished, measuring the concentration of bisphenol A in the solution after adsorption, and determining the removal rate of bisphenol A to be 80%.
The antibiotic-tetracycline hydrochloride applied to the removal of water: for the original concentration of 40 mg/L tetracycline hydrochloride solution, 500mL of the solution was placed in a stoppered conical flask. Weighing 0.5 g of the adsorbing material, putting into a conical flask, continuously stirring by using a magnetic stirrer to uniformly mix the adsorbing material and the solution, carrying out solid-liquid separation by using reduced pressure suction filtration after adsorption is finished at room temperature for 24h, and measuring the concentration of tetracycline hydrochloride in the solution after adsorption, wherein the removal rate of the tetracycline hydrochloride is 94%.
Example 2:
preparing waste clay carbon: and (3) drying the waste argil in an oven at 105 ℃ for 24h, and grinding the waste argil to a particle size of less than 0.15 mm by using a mortar. The screened spent bleaching earth particles were placed in a vacuum tube furnace and pyrolyzed for 2 h under nitrogen atmosphere (200 mL/min) at 800 ℃. And taking out the waste argil carbon after the temperature is reduced to 100 ℃.
Preparing modified waste clay carbon: 100mL of hydrofluoric acid was added to 20 g of spent bleaching clay carbon, the mixture was thoroughly mixed and left to stand for 24 hours, centrifuged, the supernatant was poured, deionized water was added thereto and centrifuged again five times in the same manner, and then the material was washed with 5000 mL of deionized water by suction filtration under reduced pressure. And (3) drying the washed material in a 65 ℃ oven for 24h to obtain the modified waste argil carbon.
Application to removal of endocrine disruptors-bisphenol A: for an initial concentration of 25 mg/L bisphenol A solution, 100mL was placed in a stoppered conical flask. Weighing 0.1 g of the adsorbing material, putting the adsorbing material into a conical flask, shaking the adsorbing material for 24 hours at room temperature and 25 ℃ by using a shaking table, recovering the material by using a filter membrane of 0.45 mu m after adsorption is finished, and measuring the concentration of bisphenol A in the solution after adsorption, wherein the removal rate of bisphenol A is 96%.
The antibiotic-oxytetracycline hydrochloride applied to the removal of water: for the original concentration of 70 mg/L of oxytetracycline hydrochloride solution, 100mL of the oxytetracycline hydrochloride solution was placed in a stoppered conical flask. And weighing 0.2 g of the adsorbing material, putting the adsorbing material into a conical flask, and shaking the adsorbing material for 24 hours by using a shaking table. After the adsorption, the material was recovered by filtration through a 0.45 μm filter membrane, and the oxytetracycline hydrochloride concentration in the solution after the adsorption was measured, the removal rate of oxytetracycline hydrochloride was 85%.
Example 3:
regeneration of modified waste clay carbon: collecting the modified waste argil carbon used in the embodiment 2 and adsorbing the endocrine disrupter bisphenol A, placing the collected modified waste argil carbon in a 65 ℃ oven to be dried for 24 hours, soaking the material in 0.1 mol/L NaOH solution for 24 hours, performing solid-liquid separation by a reduced pressure suction filtration method, washing the obtained solid to be nearly neutral by using deionized water, and placing the washed solid in the 65 ℃ oven to be dried for 24 hours to obtain the regenerated modified waste argil carbon.
Application to removal of endocrine disruptors-bisphenol A: for an initial concentration of 50 mg/L bisphenol A solution, 100mL was placed in a stoppered conical flask. Weighing 0.2 g of the regenerated spent bleaching clay carbon, putting the spent bleaching clay carbon into a conical flask, oscillating the spent bleaching clay carbon for 24 hours by using a shaking table, filtering the recovered material by using a filter membrane of 0.45 mu m after adsorption is finished, and measuring the concentration of bisphenol A in the solution after adsorption, wherein the removal rate of the bisphenol A is 78 percent.

Claims (9)

1. The preparation and use method of the modified waste carclazyte carbon for removing the endocrine disruptors and antibiotics in water is characterized in that the waste carclazyte is prepared into the waste carclazyte carbon in an anaerobic pyrolysis mode, hydrofluoric acid is used for modifying the waste carclazyte carbon to prepare the modified waste carclazyte carbon for adsorbing and removing the endocrine disruptors and the antibiotics in water, after adsorption is completed, solid-liquid separation can be realized by utilizing reduced pressure suction filtration, filtration or centrifugation, the material can be regenerated for many times after losing activity, and the regenerated material can be recycled.
2. The method for preparing and using modified waste argil charcoal for adsorbing and removing endocrine disruptors and antibiotics in water according to claim 1, wherein the endocrine disruptors to be adsorbed and removed comprise natural and synthetic hormones and degradation products thereof, and a plurality of compounds with hormonal activity from various applications, including plastic plasticizers, organic pesticides, herbicides, detergents and synthetic resin raw materials, the antibiotics comprise quinolones, macrolides, β -lactams, tetracyclines and sulfonamides, and the waste argil is obtained from the process of refining and decoloring vegetable oil.
3. The spent bleaching clay char according to claim 1, which is prepared by the following steps:
(1) drying the waste argil for 6-72 hours at the temperature of 40-105 ℃;
(2) controlling the particle size to be less than 5.0 mm by grinding or crushing;
(3) and (3) putting the waste clay particles in an oxygen-free atmosphere and at a high temperature for pyrolysis for 0.5-4 h, and taking out the waste clay particles when the temperature is lower than 100 ℃ to obtain the waste clay carbon.
4. The anaerobic pyrolysis method of claim 1, wherein the pyrolysis temperature is 300-1200 ℃, and the anaerobic atmosphere can be any one of closed system and inert gas (nitrogen or argon).
5. The method for preparing modified spent bleaching earth carbon according to claim 1, wherein the modified spent bleaching earth carbon is prepared by the following steps:
(1) drying the waste argil carbon for 6-72 hours at the temperature of 40-150 ℃;
(2) controlling the particle size to be less than 5.0 mm by grinding or crushing;
(3) fully mixing the waste argil carbon with hydrofluoric acid, and then placing for 3-72 h;
(4) carrying out solid-liquid separation on the waste argil carbon and hydrofluoric acid, and washing the rest solid;
(5) drying the washed solid for 6-72 h at the temperature of 40-150 ℃;
(6) and (3) grinding or crushing the dried solid to control the particle size to be less than 5.0 mm, thus obtaining the modified waste argil carbon.
6. The modification process of claim 1, the quality of the spent bleaching clay carbon is: the volume of hydrofluoric acid is =1g:5 mL-1 g:50 mL.
7. The use method of the modified waste argil charcoal for removing the endocrine disruptors and the antibiotics in the water according to claim 1, wherein the modified waste argil charcoal is added into the water body to be purified, which is polluted by the endocrine disruptors and/or the antibiotics, with the adding amount of 0.01-25 g/L, and then the mixture is fully and uniformly mixed, so that the adsorption time lasts for 0.5-24 h, and after the adsorption is completed, the solid-liquid separation can be realized by using reduced pressure suction filtration, filtration or centrifugation.
8. The modified spent bleaching earth charcoal for removing endocrine disruptors and antibiotics in water according to claim 1, wherein the regeneration method comprises the following steps:
(1) drying the inactivated modified waste clay carbon at 40-150 ℃ for 6-72 h;
(2) soaking the dried modified waste argil carbon in an aqueous alkali for 6-72 h;
(3) carrying out solid-liquid separation on the modified waste argil carbon and the alkali solution, and washing the rest solid;
(4) and (3) drying the washed solid for 6-72 h at the temperature of 40-150 ℃ to obtain the regenerated modified waste clay carbon.
9. The regeneration method of claim 8, wherein the alkali solution is selected from any one of sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is 0.1-5 mol/L.
CN202010008700.0A 2020-01-06 2020-01-06 Preparation and use method of modified waste argil charcoal for removing endocrine disruptors and antibiotics in water Pending CN111013541A (en)

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Application publication date: 20200417