CN107824157B - Magnetic gamma-Fe prepared by using ferro-manganese mud2O3Method for removing arsenic in water by using adsorbing material - Google Patents

Magnetic gamma-Fe prepared by using ferro-manganese mud2O3Method for removing arsenic in water by using adsorbing material Download PDF

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CN107824157B
CN107824157B CN201711211345.1A CN201711211345A CN107824157B CN 107824157 B CN107824157 B CN 107824157B CN 201711211345 A CN201711211345 A CN 201711211345A CN 107824157 B CN107824157 B CN 107824157B
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water
arsenic
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manganese
iron
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CN107824157A (en
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曾辉平
尹灿
李冬
张�杰
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Beijing University of Technology
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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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds

Abstract

The invention provides a method for preparing magnetic gamma-Fe by using ferro-manganese mud2O3A method for removing arsenic in water by using an adsorbing material. The method adopts a solvothermal synthesis mode to carry out backwashing on a biological iron and manganese removal filter tank of an underground water plant to obtain sludge, and magnetic gamma-Fe is prepared2O3The material has good adsorption effect on arsenic, can be conveniently separated from water by using a magnet, and can be recycled. The water treatment waste is recycled and used for removing arsenic pollutants in water, so that the problem of sludge disposal of a water plant can be solved, iron elements rich in the sludge are fully utilized as a resource, the medicament cost is saved, and the method has great practical significance.

Description

Magnetic gamma-Fe prepared by using ferro-manganese mud2O3Method for removing arsenic in water by using adsorbing material
The technical field is as follows:
the invention belongs to the field of environmental water treatment, and particularly relates to a method for preparing magnetic gamma-Fe by using ferro-manganese mud2O3A method for removing arsenic in water by using an adsorbing material.
Background art:
arsenic is a common toxic metalloid element in nature and can enter the human body through drinking water or through skin, digestive tract, respiratory tract, etc. If the high-arsenic water (>50 mu g/L) is drunk for a long time, arsenic can be accumulated in a human body for a long time, so that the skin, the lung, the liver, the kidney, the bladder and other organs are diseased, and the risk of teratogenesis and carcinogenesis is caused. At present, the common technical methods for removing arsenic by water treatment include a coagulating sedimentation method, an adsorption method, a biological arsenic removal method, a membrane separation method, an ion exchange method and the like. As a simple and effective arsenic removal method with simple operation, the adsorption method has a great development prospect, and the search for an adsorption material with low price, easy recovery and good adsorptivity becomes a hotspot of research.
In recent years, researchers at home and abroad have paid considerable attention to studies on adsorption performance of iron-based adsorbents and composite oxides of iron-based adsorbents and other metals on arsenic, but most of the adsorbents are prepared from pure chemical agents.
During the long-term operation of the filter tank of the iron and manganese removal water plant, especially when the iron content of the treated underground water is large, a large amount of iron oxide can be deposited under the action of the filter membrane formed on the surface of the filter material, and the iron-based iron-oxide adsorbent is an excellent iron-based adsorbent. When the iron and manganese removing filter pool is back flushed, a large amount of sludge in gaps of the filter material can be flushed out, and iron and manganese muddy water is formed. The yield of the iron-manganese mud is high, the iron content in the back washing mud is also considerable according to the iron removal mechanism, if the mud can be recycled, the method is a very effective waste recycling method, the medicament cost is saved to a certain extent, and the problem of iron-manganese mud disposal in an iron and manganese removal water plant can be effectively solved. Recent experiments show that the ferro-manganese mud powder obtained by drying, grinding and sieving the ferro-manganese mud obtained by backwashing the ferro-manganese removal filter tank of the underground water plant has good adsorption effect when being directly used for removing arsenic, but the adsorbent used for removing arsenic in water has some inevitable defects, such as difficulty in recovering the adsorbent due to difficult separation from water after treatment due to the physical form of the adsorbent.
The invention content is as follows:
in order to avoid the defects and fully utilize the water to treat the waste, the invention discloses a method for preparing magnetic gamma-Fe by using ferro-manganese mud through a solvothermal method2O3The method for removing arsenic from water by using the adsorbing material and the application thereof can rapidly realize the separation of the adsorbent from water by using an external magnetic field while ensuring good arsenic removal effect, and the recovery is simple.
The invention provides a method for preparing magnetic gamma-Fe by using iron-manganese mud2O3The method for removing arsenic in water by using the adsorption material comprises the following steps:
(1) magnetic gamma-Fe2O3And (5) preparing an adsorbing material.
Standing and precipitating the backwashing wastewater of the biological filter for removing iron and manganese in the water plant for 24-72 h, and naturally drying sludge at the bottom for later use; adding ethylene glycol and sodium acetate into the dried iron-manganese mud respectively, and fully stirring for 30-60 min to obtain a uniformly mixed suspension; putting the obtained suspension into a closed reaction kettle, heating to 160-200 ℃, and reacting for 8-14 hours at a constant temperature; naturally cooling the reaction kettle to room temperature, removing upper liquid, taking out bottom sediment, alternately cleaning with ethanol and water for 6-8 times, and separating magnetic substances from water by adopting an external magnetic field; the obtained magnetic substance is dried in a dryer to obtain magnetic powder particles.
(2) The magnetic gamma-Fe is added2O3The material is used for removing arsenic in water.
When As (III) exists in the valence state of arsenic in water, in order to achieve a better adsorption effect, adding an oxidant into the water to oxidize the As (III) into As (V), and adding a pH regulator to regulate the pH value of the solution to be 3-10; when the valence of arsenic in water is only As (V), no pre-oxidant is added. If the pH value of the solution is between 3 and 10, the pH value does not need to be adjusted; and (3) adding the magnetic powder adsorbent into the pretreated arsenic-containing water, oscillating for 24-36 h, and separating the adsorbent from the water by using a magnet.
The Fe-Mn mud used in the step (1) contains 50-95% of Fe atoms, the using amount ratio of the Fe-Mn mud, the sodium acetate and the ethylene glycol is 1g:3g: 0.03L-1 g:6g:0.06L, the drying temperature of a dryer is 40-60 ℃, and the drying time is 5-8 h.
In the step (2), the oxidant is any one of hydrogen peroxide, liquid chlorine and sodium hypochlorite. The PH regulator is HCl solution and NaOH solution, and the molar concentration is 1-3 mol/L. The ratio of the adding mass of the adsorbent to the volume of the arsenic-containing aqueous solution is 0.2 g/L-1 g/L. The arsenic content in the water to be treated is 0.01-40 mg/L.
The invention has the advantages that:
the magnetic adsorbent prepared by the invention has good adsorption performance on arsenic in water, can be easily separated from the water, has high recovery efficiency and can be repeatedly used. The material is prepared by utilizing the back washing waste mud of the iron and manganese removal water plant, so that the iron element in the high-iron groundwater is utilized, the medicament cost is saved, and the preparation method is simple and does not need harsh conditions and complicated steps. The invention provides a new way for the disposal of the sludge, and truly realizes the reclamation of the water treatment waste.
Description of the drawings:
FIG. 1 shows magnetic gamma-Fe of the present invention2O3Scanning electron microscope pictures of the surface of the adsorbing material.
FIG. 2 shows magnetic gamma-Fe of the present invention2O3Magnetic hysteresis loop of adsorbing material.
FIG. 3 shows magnetic gamma-Fe prepared from iron manganese mud according to the present invention2O3Langmuir and Freundlish isothermal model fitting curves for adsorption of materials to remove arsenic from water, where CeTo reach the concentration of As (V) in the solution at equilibrium, mg.L-1；qeMg.g to reach the limit adsorption of As (V) at saturation-1。
The specific implementation mode is as follows:
example 1 was carried out: standing and precipitating the backwash wastewater of the biofilter in the stable operation stage of the iron and manganese removal water supply plant for 24 hours, and drying sludge at the bottom for later use, wherein the atomic proportion of Fe element in the sludge is 86.6%; measuring 60mL of ethylene glycol by using a measuring cylinder, putting the ethylene glycol into a beaker, sequentially adding 2.0g of iron manganese mud and 11.0g of anhydrous sodium acetate, dissolving the mixture in the ethylene glycol, stirring for 45min to obtain a uniformly mixed suspension, putting the obtained suspension into a closed reaction kettle, heating to 180 ℃, and reacting for 10 hours at a constant temperature; naturally cooling the reaction kettle to room temperature, discarding upper liquid, taking out bottom precipitate, alternately cleaning with ethanol and water for 6 times, and separating magnetic substances from water by using a magnet; putting the obtained magnetic substance in a drier, setting the temperature at 60 ℃, and drying for 6h to obtain the magnetic gamma-Fe2O3Powder particles. The scanning electron microscope picture of the surface morphology of the adsorbent is shown in figure 1. As can be seen from the figure, the prepared magnetic adsorbent has a rough surface and a large number of pores, which is beneficial to the adsorption process.
Example 2 was carried out: standing and precipitating the backwash wastewater of the biofilter in the stable operation stage of the iron and manganese removal water supply plant for 24 hours, and drying sludge at the bottom for later use, wherein the atomic proportion of Fe element in the sludge is 80.5%; 40mL of ethylene glycol is measured by a measuring cylinderSequentially adding 1.2g of iron mud and 6.5g of anhydrous sodium acetate into a beaker, dissolving the mixture in ethylene glycol, stirring for 30min to obtain a uniformly mixed suspension, putting the obtained suspension into a closed reaction kettle, heating to 200 ℃, and reacting for 12 hours at a constant temperature; naturally cooling the reaction kettle to room temperature, discarding upper liquid, taking out bottom precipitate, alternately cleaning with ethanol and water for 8 times, and separating magnetic substances from water by using a magnet; the obtained magnetic substance was placed in a dryer, and dried at a set temperature of 50 ℃ for 7 hours to obtain magnetic powder particles. Magnetic gamma-Fe2O3The hysteresis loop of the adsorbent measured at room temperature is shown in FIG. 2. Magnetic gamma-Fe2O3The powder sorbent exhibited a typical sigmoidal magnetization curve. Saturation magnetization of 16.95 em. mu.g-1The remanent magnetization is 0.295 em. mu.g-1It has excellent paramagnetism and can be separated from water conveniently by means of external magnetic field.
Example 3 of implementation: the magnetic gamma-Fe is added2O3The adsorbent is used for removing arsenic in water. Adding 10mL of 30 volume percent hydrogen peroxide into 90mL of As (III) -containing aqueous solution to obtain a series of arsenic solutions with the concentration of 0.01-40 mg/L. The pH value of the solution is 6.3-6.8, and in the range of 3-10, no pH regulator is needed to be added. Magnetic gamma-Fe2O3Adding the powder adsorbent into pretreated arsenic-containing water at an amount of 0.2g/L, performing vibration adsorption at 25 deg.C for 24 hr, and separating the adsorbent from the water with a magnet. The adsorption capacity of the adsorbent for arsenic in water and Langmuir and Freundlish isothermal model fitting curves are shown in FIG. 3, and the maximum adsorption capacity can reach 8.7 mg/g.

Claims (3)

1. Magnetic gamma-Fe prepared by using ferro-manganese mud2O3The method for removing arsenic in water by using the adsorbing material is characterized by comprising the following steps of:
(1) magnetic gamma-Fe2O3Preparing an adsorbing material;
standing and precipitating the backwashing wastewater of the biological filter for removing iron and manganese in the water plant for 24-72 h, and naturally drying sludge at the bottom for later use; adding ethylene glycol and sodium acetate into the dried iron-manganese mud respectively, and fully stirring for 30-60 min to obtain a uniformly mixed suspension; putting the obtained suspension into a closed reaction kettle, heating to 160-200 ℃, and reacting for 8-14 hours at a constant temperature; naturally cooling the reaction kettle to room temperature, removing upper liquid, taking out bottom sediment, alternately cleaning with ethanol and water for 6-8 times, and separating magnetic substances from water by adopting an external magnetic field; drying the obtained magnetic substance in a dryer to obtain magnetic powder particles;
(2) the magnetic adsorbent is used for removing arsenic in water;
when As (III) exists in the valence state of arsenic in water, adding an oxidant into the water to oxidize the As (III) into As (V), and adding a pH regulator to regulate the pH value of the solution to be between 3 and 10; when the valence of the arsenic in the water is only As (V), a pre-oxidant is not needed to be added; if the pH value of the solution is between 3 and 10, the pH value does not need to be adjusted; adding a magnetic powder adsorbent into the pretreated arsenic-containing water, performing vibration adsorption for 24-36 h, and separating the adsorbent from the water by using a magnet;
the Fe-Mn mud used has an Fe element atom ratio of 50-95%; in the step (1), the dosage ratio of the iron manganese mud, the sodium acetate and the glycol is 1g:3g: 0.03L-1 g:6g: 0.06L;
and (2) drying for 5-8 h at the drying temperature of 40-60 ℃ in the step (1).
2. The method according to claim 1, wherein the oxidant in step (2) is any one of hydrogen peroxide, liquid chlorine and chlorine dioxide, and the pH regulator is HCl solution and NaOH solution, and the molar concentration is 1-3 mol/L.
3. The method according to claim 1, wherein the ratio of the added mass of the adsorbent to the volume of the arsenic-containing aqueous solution in the step (2) is 0.2g/L to 1g/L, and the total arsenic content in the treated water is 0.01mg/L to 40 mg/L.
CN201711211345.1A 2017-11-28 2017-11-28 Magnetic gamma-Fe prepared by using ferro-manganese mud2O3Method for removing arsenic in water by using adsorbing material Active CN107824157B (en)

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CN108940183B (en) * 2018-08-07 2020-12-22 东北师范大学 Method for preparing magnetic adsorbent by using waterworks ferro-manganese sludge as raw material
CN108940184B (en) * 2018-08-07 2021-02-02 东北师范大学 Method for preparing magnetic adsorbent by taking iron sludge of underground water plant as raw material
CN110586024A (en) * 2019-10-18 2019-12-20 北京工业大学 Arsenic removal magnetic nano adsorbent gamma-Fe prepared based on biological filter backwashing iron mud2O3Method (2)
CN111974361B (en) * 2020-07-11 2023-02-10 复旦大学 Magnetic polydopamine hexavalent chromium reduction trapping agent based on sludge carrier and preparation method thereof
CN114405456B (en) * 2022-01-20 2024-02-02 广州大学 Gamma-Fe for uranium removal 2 O 3 Preparation method of @ HAP magnetic composite material

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