CN112158932B - Magnetic zero-valent iron polyaluminum chloride composite flocculant and preparation method and application thereof - Google Patents
Magnetic zero-valent iron polyaluminum chloride composite flocculant and preparation method and application thereof Download PDFInfo
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- CN112158932B CN112158932B CN202011088095.9A CN202011088095A CN112158932B CN 112158932 B CN112158932 B CN 112158932B CN 202011088095 A CN202011088095 A CN 202011088095A CN 112158932 B CN112158932 B CN 112158932B
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
Abstract
The invention provides a magnetic zero-valent iron polyaluminum chloride composite flocculant, a preparation method and application thereof, and relates to the technical field of water treatment. The invention provides a magnetic zero-valent iron polyaluminium chloride composite flocculant which comprises 4-8% of zero-valent iron, 5-15% of ferroferric oxide, 75-85% of polyaluminium chloride and inevitable impurities in percentage by mass; the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 50-70%. The composite flocculant provided by the invention has stable quality, high basicity and certain reducibility, improves the flocculation effect, and also has a good removal effect on micro disinfection byproducts in water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a magnetic zero-valent iron polyaluminium chloride composite flocculant and a preparation method and application thereof.
Background
At present, the main methods for treating high-turbidity wastewater include a chemical method, a physical method, a biological method and the like, wherein flocculation and sedimentation in the chemical method are one of the most common methods, pollutant particles in the wastewater and a flocculating agent form large polymer floccules by adding the flocculating agent into the wastewater, and natural sedimentation of suspended particles is realized under the action of gravity, so that the aim of solid-liquid separation is fulfilled.
The traditional flocculation sedimentation process is completed under the action of gravity, the traditional flocculating agent has limited removal rate to pollutants such as suspended particles in water in the actual use process, the subsequent required mud-water separation process is longer, a larger sedimentation tank volume is required, and the initial investment cost is increased and the occupied area is increased. The traditional flocculating agent also has the major key problems of being not beneficial to separation, difficult to recover and the like. Therefore, the research and development of the flocculant which can be rapidly settled and separated and can be recycled have important application value and significance.
Disclosure of Invention
The invention aims to provide a magnetic zero-valent iron polyaluminium chloride composite flocculant as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a magnetic zero-valent iron polyaluminium chloride composite flocculant which comprises 4-8% of zero-valent iron, 5-15% of ferroferric oxide, 75-85% of polyaluminium chloride and inevitable impurities in percentage by mass; the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 50-70%.
Preferably, the magnetic zero-valent iron polyaluminum chloride composite flocculant comprises a carrier and polyaluminum chloride loaded on the carrier; the carrier comprises ferroferric oxide and zero-valent iron.
The invention also provides a preparation method of the magnetic zero-valent iron polyaluminium chloride composite flocculant in the technical scheme, which comprises the following steps:
mixing the aluminum-iron alloy waste with a sodium hydroxide solution, and carrying out an oxidation-reduction reaction to obtain a reaction solution and a solid product; the reaction liquid comprises hydroxyl ions and meta-aluminate ions; the solid product comprises zero-valent iron and ferroferric oxide;
and adding waste hydrochloric acid into the reaction liquid and the solid product to enable the pH value of the system to be 3.5-5.0, and carrying out polymerization reaction to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant.
Preferably, the ratio between the mass of the ferroaluminium scrap and the mass of sodium hydroxide in the sodium hydroxide solution is 1 g: 0.05 to 0.1 mol.
Preferably, the mass content of iron in the aluminum-iron alloy waste is 10-40%.
Preferably, the concentration of the sodium hydroxide solution is 1-5 mol/L.
Preferably, the temperature of the oxidation-reduction reaction is 70-100 ℃ and the time is 0.5-6 h.
Preferably, the concentration of hydrogen chloride in the waste hydrochloric acid is 1-5 mol/L; the waste hydrochloric acid is from acid-washing waste hydrochloric acid of an aluminum plant.
Preferably, the temperature of the polymerization reaction is 60-100 ℃, and the time is 4-6 h.
The invention also provides the application of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the technical scheme or the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the preparation method in sewage treatment.
The invention provides a magnetic zero-valent iron polyaluminium chloride composite flocculant which comprises 4-8% of zero-valent iron, 5-15% of ferroferric oxide, 75-85% of polyaluminium chloride and inevitable impurities in percentage by mass; the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 50-70%. In the invention, zero-valent iron has a unique core-shell structure, the mechanism of removing heavy metal is mainly divided into reduction reaction, adsorption reaction and precipitation/coprecipitation reaction, iron oxide is covered by hydroxyl in water in the reaction process, heavy metal ions to be removed are adsorbed to the surface of the zero-valent iron through complexation and electrostatic action, iron at the central position is equivalent to a reducing agent with strong capacity to provide electrons required for the reaction, so that the heavy metal is reduced to a lower valence state, and the heavy metal ions with the low valence state react with OH < - > to generate precipitation or coprecipitation under the alkaline condition, so that the heavy metal ions can be removed; the single polyaluminium chloride has the removal effect on both organic matters and heavy metals, and the addition of the zero-valent iron further improves the removal effect on the organic matters and the heavy metals, particularly the heavy metals; the ferroferric oxide has stronger magnetism, the ferroferric oxide is compounded with zero-valent iron and polyaluminium chloride, the flocculation sedimentation speed can be obviously improved, the mud-water separation time is shortened, and the magnetic flocculant can realize rapid solid-liquid separation under the condition of an external magnetic field, thereby being beneficial to the separation and recovery of the composite flocculant.
The invention also provides a preparation method of the magnetic zero-valent iron polyaluminium chloride composite flocculant, which comprises the following steps: mixing the aluminum-iron alloy waste with a sodium hydroxide solution, and carrying out an oxidation-reduction reaction to obtain a reaction solution and a solid product; the reaction liquid comprises hydroxyl ions and meta-aluminate ions; the solid product comprises zero-valent iron and ferroferric oxide; and adding waste hydrochloric acid into the reaction liquid and the solid product to enable the pH value of the system to be 3.5-5.0, and carrying out polymerization reaction to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant. In the invention, aluminum in the aluminum-iron alloy waste reacts with sodium hydroxide to generate sodium metaaluminate, and part of zero-valent iron in the aluminum-iron alloy waste is oxidized into ferroferric oxide; after the waste hydrochloric acid is added, the pH value of the system is controlled to be 3.5-5.0, sodium metaaluminate is hydrolyzed to generate aluminum hydroxide under an acidic condition, and the aluminum hydroxide reacts with the hydrochloric acid to generate polyaluminium chloride. The preparation method provided by the invention has the advantages of simple process flow, convenience in operation, short preparation time and high basicity, and can improve the flocculation effect. The magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the invention has the advantages of no chemical agent pollution, low cost and high recovery rate when in use, can greatly reduce the volume of a sedimentation tank, and saves the investment cost and the occupied area, thereby providing a novel and effective composite flocculant for a coagulation treatment process of purified water and sewage.
The magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the invention can be widely applied to the treatment of inorganic wastewater containing phosphorus, heavy metal ions and the like and the treatment of organic wastewater with more suspended matters and high turbidity in enterprises in industries such as papermaking, food processing, breeding, petrochemical industry and the like.
The magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the invention can effectively remove disinfection byproducts in water and has beneficial effects on the health of residents.
The invention seeks a new resource method for the waste hydrochloric acid and the alloy waste, reduces the environmental pressure and has better social benefit and economic benefit.
Drawings
FIG. 1 is a flow chart of a preparation process of a magnetic zero-valent iron polyaluminum chloride composite flocculant in an embodiment of the invention;
FIG. 2 is an XRD diagram of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared in example 2 of the present invention.
Detailed Description
The invention provides a magnetic zero-valent iron polyaluminium chloride composite flocculant which comprises 4-8% of zero-valent iron, 5-15% of ferroferric oxide, 75-85% of polyaluminium chloride and inevitable impurities in percentage by mass; the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 50-70%.
In the invention, the magnetic zero-valent iron polyaluminium chloride composite flocculant more preferably comprises 5-6% of zero-valent iron, 13-14% of ferroferric oxide, 76-80% of polyaluminium chloride and inevitable impurities in percentage by mass.
In the invention, the unavoidable impurities preferably comprise insoluble impurities and soluble salts, the insoluble impurities are mainly silicon, and the mass of the insoluble impurities preferably accounts for 0.01-0.3% of the total mass of the magnetic zero-valent iron polyaluminium chloride composite flocculant, and more preferably accounts for 0.02-0.08%; the soluble salt preferably comprises sodium chloride, and the mass of the soluble salt preferably accounts for 0.1-1.5% of the total mass of the magnetic zero-valent iron polyaluminum chloride composite flocculant, and more preferably 0.1-0.5%.
In the invention, the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 50-70%, and preferably 60-70%.
In the present invention, the magnetic zero-valent iron polyaluminum chloride composite flocculant preferably comprises a carrier and polyaluminum chloride supported on the carrier; the carrier comprises ferroferric oxide and zero-valent iron.
The invention provides a preparation method of a magnetic zero-valent iron polyaluminium chloride composite flocculant, which comprises the following steps:
mixing the aluminum-iron alloy waste with a sodium hydroxide solution, and carrying out an oxidation-reduction reaction to obtain a reaction solution and a solid product; the reaction liquid comprises hydroxyl ions and meta-aluminate ions; the solid product comprises zero-valent iron and ferroferric oxide;
and adding waste hydrochloric acid into the reaction liquid and the solid product to enable the pH value of the system to be 3.5-5.0, and carrying out polymerization reaction to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant.
In the present invention, the raw materials used are all commercially available products well known to those skilled in the art, unless otherwise specified.
The invention mixes the aluminum-iron alloy waste material and the sodium hydroxide solution to carry out oxidation-reduction reaction to obtain reaction liquid and solid products. In the present invention, the source of the ferroaluminum alloy scrap is preferably an alloy factory; the mass content of iron in the aluminum-iron alloy waste is preferably 10-40%, and more preferably 20-30%. In the present invention, the aluminum-iron alloy scrap preferably contains zero-valent iron, and the mass content of the zero-valent iron is preferably 5%.
In the invention, the concentration of the sodium hydroxide solution is preferably 1-5 mol/L, and more preferably 2-4 mol/L.
In the present invention, the ratio of the mass of the aluminum-iron alloy scrap to the mass of sodium hydroxide in the sodium hydroxide solution is preferably 1 g: 0.05 to 0.1 mol.
In the invention, the temperature of the oxidation-reduction reaction is preferably 70-100 ℃, and more preferably 90 ℃; the time of the oxidation-reduction reaction is preferably 0.5-6 h, and more preferably 2-4 h.
In the present invention, the chemical reaction occurring during the redox reaction includes:
2Al+2H2O+2NaOH＝＝2NaAlO2+3H2↑；
3Fe+2O2＝Fe3O4。
in the invention, the reaction liquid comprises hydroxide ions and meta-aluminate ions; the solid product comprises zero-valent iron and ferroferric oxide.
After reaction liquid and solid products are obtained, waste hydrochloric acid is added into the reaction liquid and the solid products to enable the pH value of the system to be 3.5-5.0, and polymerization reaction is carried out to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant. In the invention, the source of the waste hydrochloric acid is preferably acid-washing waste hydrochloric acid of an aluminum plant; the concentration of the hydrogen chloride in the waste hydrochloric acid is preferably 1-5 mol/L, and more preferably 2-4 mol/L.
In the present invention, the method of adding the waste hydrochloric acid to the reaction solution and the solid product preferably comprises: firstly, carrying out ultrasonic dispersion on the reaction liquid and the solid product, and then adding waste hydrochloric acid under the stirring condition to ensure that the pH value of the system is 3.5-5.0. The invention has no special requirements on the power and stirring parameters of the ultrasonic dispersion, and the process which is well known by the technical personnel in the field can be adopted. In the invention, the pH value of the system is preferably 4-5.
In the invention, the temperature of the polymerization reaction is preferably 60-100 ℃, and more preferably 70-90 ℃; the time of the polymerization reaction is preferably 4-6 h.
In the present invention, the chemical reactions that occur during the polymerization reaction include:
NaAlO2+HCl+H2O＝Al(OH)3↓+NaCl
(6-n)HCl+2Al(OH)3＝Al2(OH)nCl6-n+(6-n)H2O
mAl2(OH)nCl6-n＝＝[Al2(OH)nCl6-n]m
according to the invention, preferably, after the polymerization reaction, the obtained system is washed and filtered, and then the obtained solid substance is dried to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant. In the invention, the washing is preferably carried out by using deionized water; the drying is preferably vacuum drying, the temperature of the drying is preferably 60 ℃, and the time is preferably 12 hours.
The invention also provides an application of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared by the technical scheme or the preparation method in sewage treatment, and the magnetic zero-valent iron polyaluminum chloride composite flocculant is particularly applied to treatment of inorganic wastewater and organic wastewater. In the invention, the usage amount of the magnetic zero-valent iron polyaluminium chloride composite flocculant is preferably 10-50 mg/L, and more preferably 20-25 mg/L.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 1mol/L sodium hydroxide solution, and after stirring reaction is carried out for 2 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 5.9% of zero-valent iron, 13.7% of ferroferric oxide, 79.3% of polyaluminum chloride, 0.05% of insoluble impurities and the balance of sodium chloride, and the basicity is 57%.
Example 2
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 2mol/L sodium hydroxide solution, and after stirring reaction is carried out for 2 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 6.3% of zero-valent iron, 12.8% of ferroferric oxide, 80.2% of polyaluminum chloride, 0.02% of insoluble impurities and the balance of sodium chloride, and the basicity is 64%.
Example 3
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 3mol/L sodium hydroxide solution, and after stirring reaction is carried out for 2 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 5.9% of zero-valent iron, 14.1% of ferroferric oxide, 79.4% of polyaluminum chloride, 0.08% of insoluble impurities and the balance of sodium chloride, and the basicity is 61%.
Example 4
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of sodium hydroxide solution with the concentration of 4mol/L, and after stirring reaction is carried out for 2 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 5.8% of zero-valent iron, 13.9% of ferroferric oxide, 79.0% of polyaluminum chloride, 0.11% of insoluble impurities and the balance of sodium chloride, and the basicity is 60%.
Example 5
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of sodium hydroxide solution with the concentration of 5mol/L, and after stirring reaction is carried out for 2 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 5.9% of zero-valent iron, 13.8% of ferroferric oxide, 78.1% of polyaluminum chloride, 0.18% of insoluble impurities and the balance of sodium chloride, and the basicity is 58%.
Example 6
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 2mol/L sodium hydroxide solution, and after stirring reaction is carried out for 4 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 4h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 4.8% of zero-valent iron, 13.7% of ferroferric oxide, 79.2% of polyaluminum chloride, 0.18% of insoluble impurities and the balance of sodium chloride, and the basicity is 60%.
Example 7
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 2mol/L sodium hydroxide solution, and after stirring reaction is carried out for 4 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 6h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 4.8% of zero-valent iron, 13.8% of ferroferric oxide, 80.3% of polyaluminum chloride, 0.11% of insoluble impurities and the balance of sodium chloride, and the basicity is 63%.
Example 8
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 10 wt% is added into 100mL of 2mol/L sodium hydroxide solution, and after stirring reaction is carried out for 4 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 4, carrying out polymerization reaction for 6h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 4.1% of zero-valent iron, 8.9% of ferroferric oxide, 85.5% of polyaluminum chloride, 0.12% of insoluble impurities and the balance of sodium chloride, and the basicity is 62%.
Example 9
Under the condition of the temperature of 90 ℃, 2g of aluminum-iron alloy waste with the iron content of 20 wt% is added into 100mL of 2mol/L sodium hydroxide solution, and after stirring reaction is carried out for 4 hours, zero-valent iron, ferroferric oxide and sodium metaaluminate solution are obtained; adding waste hydrochloric acid (the mass content of hydrogen chloride is 6.2%) while stirring, adjusting the pH value to 5, carrying out polymerization reaction for 6h at 70 ℃, washing and filtering the obtained sample by deionized water, and carrying out vacuum drying for 12h at 60 ℃ to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant; the magnetic zero-valent iron polyaluminium chloride composite flocculant consists of zero-valent iron, ferroferric oxide and polyaluminium chloride, and the polyaluminium chloride is loaded by taking the ferroferric oxide and the zero-valent iron as carriers; by mass percentage, the composite flocculant contains 5.2% of zero-valent iron, 14.9% of ferroferric oxide, 76.8% of polyaluminum chloride, 0.21% of insoluble impurities and the balance of sodium chloride, and the basicity is 54%.
Test example 1
(1) Flocculation test:
the wastewater adopted in the test comes from domestic sewage of a municipal sewage treatment plant, and the water quality conditions are as follows: 40mg/L suspended matter, 120 times chroma, 50 degrees turbidity and 1.54mg/L total phosphorus;
25mg of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared in examples 1 to 5 was added to 1000mL of the wastewater, and the removal rate of each water quality parameter was calculated as shown in Table 1.
TABLE 1 indexes and removal rates of treated wastewater
As can be seen from Table 1, the composite flocculant prepared by the invention has excellent treatment effect on target wastewater, and the synthesis method of the embodiment is proved to be feasible and effective.
(2) Chloroform removal test:
in the test, trichloromethane is adopted to simulate the wastewater, and the concentration of the trichloromethane is 10 ppm;
25mg of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared in examples 1 to 5 was added to 1000mL of the simulated wastewater, and the removal rate of chloroform was calculated as shown in Table 2.
TABLE 2 removal of chloroform
As can be seen from Table 2, the composite flocculant prepared by the invention has excellent treatment effect on the disinfection by-product trichloromethane, and the synthetic method of the embodiment is proved to be feasible and effective.
Test example 2
An XRD pattern of the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared in example 2 is shown in fig. 2, and it can be seen from fig. 2 that the magnetic zero-valent iron polyaluminum chloride composite flocculant prepared in the present invention is composed of zero-valent iron, ferroferric oxide and polyaluminum chloride.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The application of the magnetic zero-valent iron polyaluminium chloride composite flocculant in the treatment of trichloromethane sewage comprises, by mass, 4-8% of zero-valent iron, 5-15% of ferroferric oxide, 75-85% of polyaluminium chloride and inevitable impurities; the basicity of the magnetic zero-valent iron polyaluminium chloride composite flocculant is 57-70%;
the magnetic zero-valent iron polyaluminium chloride composite flocculant comprises a carrier and polyaluminium chloride loaded on the carrier; the carrier comprises ferroferric oxide and zero-valent iron;
the preparation method of the magnetic zero-valent iron polyaluminium chloride composite flocculant comprises the following steps:
mixing the aluminum-iron alloy waste with a sodium hydroxide solution, and carrying out an oxidation-reduction reaction to obtain a reaction solution and a solid product; the reaction liquid comprises hydroxyl ions and meta-aluminate ions; the solid product comprises zero-valent iron and ferroferric oxide;
and adding waste hydrochloric acid into the reaction liquid and the solid product to enable the pH value of the system to be 3.5-5.0, and carrying out polymerization reaction to obtain the magnetic zero-valent iron polyaluminium chloride composite flocculant.
2. Use according to claim 1, wherein the ratio between the mass of the ferroaluminium scrap and the mass of sodium hydroxide in the sodium hydroxide solution is 1 g: 0.05 to 0.1 mol.
3. The use according to claim 1 or 2, wherein the mass content of iron in the ferroaluminum alloy scrap is 10-40%.
4. The use according to claim 1 or 2, wherein the concentration of the sodium hydroxide solution is 1 to 5 mol/L.
5. The use according to claim 1, wherein the temperature of the redox reaction is 70-100 ℃ and the time is 0.5-6 h.
6. The use according to claim 1, wherein the concentration of hydrogen chloride in the waste hydrochloric acid is 1-5 mol/L; the waste hydrochloric acid is from acid-washing waste hydrochloric acid of an aluminum plant.
7. The use according to claim 1, wherein the polymerization is carried out at a temperature of 60 to 100 ℃ for 4 to 6 hours.
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