CN110894084A - Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage - Google Patents
Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage Download PDFInfo
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- CN110894084A CN110894084A CN201911241916.5A CN201911241916A CN110894084A CN 110894084 A CN110894084 A CN 110894084A CN 201911241916 A CN201911241916 A CN 201911241916A CN 110894084 A CN110894084 A CN 110894084A
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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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention belongs to the field of water treatment, and particularly relates to a nano zero-valent iron load material, a preparation method thereof and a purification method of hexavalent chromium in sewage. The nano zero-valent iron load material provided by the invention comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid. The humic acid is used as a carrier material of the nano zero-valent iron, has the property of a carbon material, can provide powerful attachment sites for the nano zero-valent iron, and effectively avoids the agglomeration of the nano zero-valent iron; moreover, the humic acid has stronger adsorption capacity to metal ions, can reduce the oxidation and dissolution of iron ions in the process of reducing hexavalent chromium by zero-valent iron, and can adsorb reduced trivalent chromium, thereby greatly reducing the concentration of residual iron ions and chromium ions in the sewage. Compared with the traditional nano zero-valent iron particles, the nano zero-valent iron load material provided by the invention has relatively larger particle size and is easier to separate and recover from a water body.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a nano zero-valent iron load material, a preparation method thereof and a purification method of hexavalent chromium in sewage.
Background
Heavy metal-caused water pollution is a very common and serious problem, and among heavy metal pollution, hexavalent chromium is the most common one, and is mainly generated from industrial pollution, such as electroplating rinse wastewater, tanning wastewater, metal processing wastewater and the like. Chromium is a heavy metal, frequently in the valence states +2, +3 and +6, and exists mainly in the forms of +3 and +6 in an aqueous environment, wherein the toxicity of cr (vi) is 100 times that of cr (iii), and hexavalent chromium cr (vi) is considered toxic and carcinogenic and may cause some health problems such as asthma, internal bleeding, dermatitis, kidney and liver damage, and nausea.
Currently, there are mainly physical, chemical and biological methods for hexavalent chromium removal. The physical method for treating hexavalent chromium comprises methods such as ion exchange, membrane filtration, adsorption and the like, wherein the ion exchange and the membrane filtration are expensive and are generally only applied to special occasions. Thus, physical treatment methods are mainly based on adsorption, but physical adsorption still has the disadvantage of limited adsorption capacity, and the treatment cost is increased significantly for some scarce raw materials. The bioremediation process is to convert harmful pollutants into non-toxic compounds and has the advantages of low energy demand, low operation cost, no harm to the environment and health, high efficiency, reusability, metal recovery and the like, and microorganisms which have been able to reduce hexavalent chromium at present include aerobic bacteria, anaerobic bacteria and part of fungi, even though the types of microorganisms which have been found to be able to treat hexavalent chromium at present are few, the concentration of treated hexavalent chromium is low, and thus the practical application is often limited. Chemical methods are the main means of removing hexavalent chromium that are commonly used at present. Chemical repair is the reduction of cr (vi) to cr (iii) using chemicals commonly used are: sulfur dioxide, sodium bisulfite, ferrous sulfate, ferrous chloride, etc. When the substances are adopted for hexavalent chromium restoration, a large amount of excess sludge is easily generated, and the management, transportation and final disposal of the excess sludge and the related cost are difficult. When the treatment is carried out by a chemical method, an electrochemical method, such as electro-dissolution, electro-flocculation and the like, can be adopted for treatment, but the method is not ideal for removing hexavalent chromium and has higher requirements on electrodes and pH. Among all the methods, nano zero-valent iron is being widely studied as an emerging treatment means for hexavalent chromium.
The main principle of processing hexavalent chromium by nano zero-valent iron is adsorption reduction precipitation, and the reduction precipitation seems to be a method capable of reducing the toxicity of hexavalent chromium to the maximum extent, because the method can reduce hexavalent chromium into trivalent chromium in a very short time and continuously adsorb the trivalent chromium, and the spread of the toxicity of hexavalent chromium is controlled in a limited time. Among reduction methods, nano zero-valent iron (nZVI) is one of the most effective materials for in-situ remediation of wastewater. Compared with the traditional zero-valent iron (ZVI) particles, the nZVI has higher specific surface area, stronger surface activity and wide applicability. nZVI is widely used for in situ remediation of cr (vi) -contaminated groundwater because it is lower cost, faster, more efficient and more environmentally friendly than conventional ZVI, ferrous sulfate and calcium polysulfides.
However, due to the large specific surface area and ultra-high surface energy of the nanoparticles, coupled with van der waals forces and magnetic properties, nZVI particles often form aggregates, thereby greatly reducing their propagation in contaminated groundwater and soil, and when nZVI is not in contact with target contaminants, oxidation often occurs, resulting in deactivation of nZVI. In addition, when the nano zero-valent iron is used for treating the heavy metal hexavalent chromium, iron ions are easy to dissolve out, and nano particles without dissolved iron ions are difficult to separate in a solution, so that the secondary pollution condition is easy to occur after the treatment.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a nano zero-valent iron load material, a preparation method thereof, and a purification method of hexavalent chromium in sewage, in which the nano zero-valent iron load material provided by the present invention can efficiently remove hexavalent chromium in a water body, iron ions are not easily dissolved out during hexavalent chromium removal, and the separation and recovery difficulty is low after hexavalent chromium removal.
The invention provides a nano zero-valent iron load material which comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid.
Preferably, the nano zero-valent iron particles completely wrap the surface of the humic acid to form a zero-valent iron layer.
Preferably, the diameter of the nanometer zero-valent iron particle is 0.1-1 nm.
The invention provides a preparation method of a nano zero-valent iron load material, which comprises the following steps:
a) mixing water-soluble ferrous salt and humic acid in water to obtain a mixed solution;
b) and in the atmosphere of protective gas, mixing the mixed solution with a reducing agent for reaction to obtain the nano zero-valent iron load material.
Preferably, in step a), the water-soluble ferrous salt comprises ferrous sulfate.
Preferably, in the step a), the mass ratio of the iron element to the humic acid in the water-soluble ferrous salt is 1: (0.2 to 3); the content of iron element in the water-soluble ferrous salt in water is 0.025-0.1 mol/L.
Preferably, in step b), the reducing agent comprises sodium borohydride.
Preferably, in the step b), the temperature of the mixing reaction is 15-35 ℃; the mixing reaction time is 0.5-1.5 h.
Preferably, step b) specifically comprises:
and stirring the mixed solution in a protective gas atmosphere, dropwise adding a reducing agent aqueous solution into the mixed solution, and continuously stirring for reaction after the dropwise adding is finished to obtain the nano zero-valent iron load material.
The invention provides a method for purifying hexavalent chromium in sewage, which comprises the following steps:
the nano zero-valent iron load material or the nano zero-valent iron load material prepared by the preparation method of the technical scheme is added into sewage containing hexavalent chromium, and the nano zero-valent iron load material removes the hexavalent chromium in the sewage to obtain purified water.
Compared with the prior art, the invention provides a nano zero-valent iron load material, a preparation method thereof and a purification method of hexavalent chromium in sewage. The nano zero-valent iron load material provided by the invention comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid. The humic acid is used as a carrier material of the nano zero-valent iron, has the property of a carbon material, can provide powerful attachment sites for the nano zero-valent iron, and effectively avoids the agglomeration of the nano zero-valent iron; and the humic acid has stronger adsorption capacity to metal ions, can reduce the oxidation and dissolution of iron ions in the process of reducing hexavalent chromium by zero-valent iron, and can adsorb the reduced trivalent chromium, thereby greatly reducing the concentration of residual iron ions and chromium ions in the sewage and reducing secondary pollution. Compared with the traditional nano zero-valent iron particles, the nano zero-valent iron load material provided by the invention has relatively large particle size, so that the nano zero-valent iron load material is easier to separate and recover from a water body, and further the risk of secondary pollution is further reduced. The nano zero-valent iron load material provided by the invention combines humic acid and nano zero-valent iron, exerts the capability of removing heavy metals of the two materials to the maximum extent, has an excellent removing effect on hexavalent chromium in water, and has a very wide application prospect in the field of sewage chromium treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of purified humic acid and nano zero-valent iron loaded material provided in example 1 of the present invention;
FIG. 2 is an X-ray diffraction diagram of nano zero-valent iron particles and a nano zero-valent iron supporting material provided by the invention;
FIG. 3 is a graph showing the effect of different dosages of nano zero-valent iron loading material on removing hexavalent chromium according to the embodiment 2 of the present invention;
FIG. 4 is a graph comparing the removal of hexavalent chromium with different materials provided in example 3 of the present invention;
FIG. 5 is an SEM image of a nano zero-valent iron supporting material after reaction with hexavalent chromium, provided by example 3 of the present invention;
FIG. 6 is an X-ray energy dispersion spectrum of a nano zero-valent iron-supporting material after reaction with hexavalent chromium, provided in example 3 of the present invention;
FIG. 7 is a comparative graph showing the hexavalent chromium removal effect of the nano zero-valent iron supporting material provided in example 4 of the present invention under different pH conditions;
fig. 8 is a comparative graph of hexavalent chromium removal effects of different nano zero-valent iron loading materials provided in example 10 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
The invention provides a nano zero-valent iron load material which comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid.
The nano zero-valent iron load material provided by the invention comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid. Wherein the particle size of the humic acid is preferably less than or equal to 23 μm; the diameter of the nanometer zero-valent iron particle is preferably 0.1-1 nm, and specifically can be 0.1nm, 0.15nm, 0.2nm, 0.25nm, 0.3nm, 0.35nm, 0.4nm, 0.45nm, 0.5nm, 0.55nm, 0.6nm, 0.65nm, 0.7nm, 0.75nm, 0.8nm, 0.85nm, 0.9nm, 0.95nm or 1 nm; the nano zero-valent iron particles preferably completely wrap the surface of the humic acid to form a zero-valent iron layer.
The humic acid is used as a carrier material of the nano zero-valent iron, has the property of a carbon material, can provide powerful attachment sites for the nano zero-valent iron, and effectively avoids the agglomeration of the nano zero-valent iron; and the humic acid has stronger adsorption capacity to metal ions, can reduce the oxidation and dissolution of iron ions in the process of reducing hexavalent chromium by zero-valent iron, and can adsorb the reduced trivalent chromium, thereby greatly reducing the concentration of residual iron ions and chromium ions in the sewage and reducing secondary pollution. Compared with the traditional nano zero-valent iron particles, the nano zero-valent iron load material provided by the invention has relatively large particle size, so that the nano zero-valent iron load material is easier to separate and recover from a water body, and further the risk of secondary pollution is further reduced. The nano zero-valent iron load material provided by the invention combines humic acid and nano zero-valent iron, exerts the capability of removing heavy metals of the two materials to the maximum extent, has an excellent removing effect on hexavalent chromium in water, and has a very wide application prospect in the field of sewage chromium treatment.
The invention also provides a preparation method of the nano zero-valent iron load material, which comprises the following steps:
a) mixing water-soluble ferrous salt and humic acid in water to obtain a mixed solution;
b) and in the atmosphere of protective gas, mixing the mixed solution with a reducing agent for reaction to obtain the nano zero-valent iron load material.
In the preparation method provided by the invention, firstly, humic acid and water-soluble ferrous salt are mixed in water. Wherein the particle size of the humic acid is preferably less than or equal to 23 μm. In the present invention, the humic acid is preferably subjected to a purification treatment before being mixed, and the specific steps of the purification treatment preferably include:
dissolving the humic acid crude product in alkali liquor, and filtering to obtain filtrate; then mixing the filtrate with acid to obtain precipitated solid; and finally, cleaning and drying the precipitated solid to obtain the purified humic acid.
In the purification step of humic acid provided by the invention, the alkali liquor is preferably an aqueous solution of sodium hydroxide, and the concentration of the aqueous solution of sodium hydroxide is preferably 0.05-0.2 mol/L, and specifically may be 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L, 0.19mol/L or 0.2 mol/L; the acid is preferably hydrochloric acid; the pH value of the filtrate mixed with the acid is preferably 1-3, and specifically can be 1, 1.2, 1.5, 1.7, 2, 2.3, 2.5, 2.7 or 3; the washing agent for cleaning is preferably an acid solution, more preferably an aqueous hydrochloric acid solution, and the concentration of the aqueous hydrochloric acid solution is preferably 0.05-0.2 mol/L, and specifically can be 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L, 0.19mol/L or 0.2 mol/L; the drying mode is preferably freeze drying, and the drying time is preferably 24-48 h.
In the preparation method provided by the invention, in the process of mixing humic acid and water-soluble ferrous salt in water, the water-soluble ferrous salt preferably comprises ferrous sulfate; the mass ratio of the iron element to the humic acid in the water-soluble ferrous salt is preferably 1: (0.2-3), specifically 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.25, 1:1.5, 1:1.75, 1:2, 1:2.25, 1:2.5, 1:2.75 or 1: 3; the content of iron element in the water-soluble ferrous salt in water is preferably 0.025-0.1 mol/L, and specifically can be 0.025mol/L, 0.03mol/L, 0.035mol/L, 0.04mol/L, 0.045mol/L, 0.05mol/L, 0.055mol/L, 0.06mol/L, 0.065mol/L, 0.07mol/L, 0.075mol/L, 0.08mol/L, 0.085mol/L, 0.09mol/L, 0.095mol/L or 0.1 mol/L. In the present invention, the mixing is preferably performed by first performing ultrasonic mixing and then performing stirring mixing. Wherein the ultrasonic mixing temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the ultrasonic mixing time is preferably 0.5-2 h, and specifically can be 0.5h, 1h, 1.5h or 2 h; the stirring and mixing temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the rotation speed of the stirring and mixing is preferably 300-100 rpm, and specifically can be 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm or 1000 rpm; the stirring and mixing time is preferably 3-12 h, and specifically can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In the preparation method provided by the invention, water-soluble ferrous salt and humic acid are uniformly mixed in water to obtain a mixed solution, and then the mixed solution and a reducing agent are mixed and react in a protective gas atmosphere. Wherein the protective gas is preferably nitrogen; the reducing agent preferably comprises sodium borohydride; the molar ratio of the sodium borohydride to the iron element in the mixed solution is preferably (3-6): 1, specifically 3:1, 4:1, 5:1 or 6: 1; the temperature of the mixing reaction is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the mixing reaction time is preferably 0.5-1.5 h, and specifically can be 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h, 1h, 1.05h, 1.1h, 1.15h, 1.2h, 1.25h, 1.3h, 1.35h, 1.4h, 1.45h or 1.5 h. In one embodiment provided by the present invention, the mixing reaction is preferably performed according to the following steps:
and stirring the mixed solution in a protective gas atmosphere, dropwise adding a reducing agent aqueous solution into the mixed solution, and continuing stirring for reaction after the dropwise adding is finished.
In the mixing reaction step provided by the invention, the rotation speed of stirring in the dropwise adding process and after the dropwise adding is finished is preferably 300-100 rpm independently, and specifically can be 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm or 1000 rpm; the concentration of the reducing agent aqueous solution is preferably 0.1-0.3 mol/L, and specifically can be 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L, 0.19mol/L, 0.2mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L, 0.25mol/L, 0.26mol/L, 0.27mol/L, 0.28mol/L, 0.29mol/L or 0.3 mol/L; the dropping speed of the reducing agent aqueous solution is preferably 0.5-2 mL/min, and specifically can be 0.5mL/min, 0.6mL/min, 0.7mL/min, 0.8mL/min, 0.9mL/min, 1mL/min, 1.1mL/min, 1.2mL/min, 1.3mL/min, 1.4mL/min, 1.5mL/min, 1.6mL/min, 1.7mL/min, 1.8mL/min, 1.9mL/min or 2 mL/min; the time for continuing stirring is preferably 10-30 min, and specifically may be 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30 min.
In the preparation method provided by the invention, after the mixed solution and the reducing agent are mixed and reacted, the nano zero-valent iron load material is obtained, and then the nano zero-valent iron load material generated by the reaction is separated from the reaction system, washed and dried, so that the pure nano zero-valent iron load material product can be obtained. Wherein, the separation mode is preferably magnetic adsorption separation; the washing agent is preferably oxygen-free deionized water; the drying mode is preferably freeze drying; the drying time is preferably 24-48 h.
According to the preparation method provided by the invention, the mixed solution containing humic acid and ferrous salt is subjected to liquid phase reduction, so that nano zero-valent iron particles generated by reduction are uniformly dispersed and adsorbed on the surface of the humic acid, and thus the nano zero-valent iron load material is obtained. The preparation method combines humic acid and nano zero-valent iron, exerts the removing capability of two materials on heavy metals to the maximum extent, has very excellent removing effect on hexavalent chromium in water, and has very wide application prospect in the field of sewage chromium treatment. More specifically, the preparation method provided by the invention has at least the following advantages:
1) humic acid is used as a carrier material of the nano zero-valent iron, has the property of a carbon material, can provide a powerful attachment site for the nano zero-valent iron, and effectively avoids the agglomeration of the nano zero-valent iron; and the humic acid has stronger adsorption capacity to metal ions, can reduce the oxidation and dissolution of iron ions in the process of reducing hexavalent chromium by zero-valent iron, and can adsorb the reduced trivalent chromium, thereby greatly reducing the concentration of residual iron ions and chromium ions in the sewage and reducing secondary pollution.
2) The nano zero-valent iron particles formed by reduction are uniformly dispersed and do not agglomerate, have larger specific surface area and smaller particle size, and have promotion effect on efficiently removing hexavalent chromium in water.
3) Compared with the traditional nano zero-valent iron particles, the nano zero-valent iron load material prepared by the method has relatively large particle size, so that the nano zero-valent iron load material is easier to separate and recover from a water body, and the risk of secondary pollution is further reduced.
4) Simple preparation steps, low raw material cost, mild conditions and safe operation process, thereby being very easy to popularize and popularize.
The invention also provides a purification method of hexavalent chromium in sewage, which comprises the following steps:
the nano zero-valent iron load material or the nano zero-valent iron load material prepared by the preparation method of the technical scheme is added into sewage containing hexavalent chromium, and the nano zero-valent iron load material removes the hexavalent chromium in the sewage to obtain purified water.
In the purification method provided by the invention, the nano zero-valent iron load material is directly added into the sewage containing hexavalent chromium, the nano zero-valent iron load material removes (adsorbs and reduces) the hexavalent chromium in the sewage, and after a period of time, the nano zero-valent iron load material is separated from the water body to obtain the purified water after chromium removal.
The purification method provided by the invention adopts the nano zero-valent iron load material provided by the invention to treat the chromium-containing sewage, so that the method has very excellent hexavalent chromium removal effect and has very wide application prospect in the field of sewage chromium treatment.
For the sake of clarity, the following examples are given in detail.
Example 1
A nanometer zero-valent iron load material takes humic acid as a carrier, nanometer zero-valent iron particles are loaded on the surface of the humic acid, and the preparation process specifically comprises the following steps:
(1) purification of humic acid
Weighing 5g of crude humic acid (Aike reagent, purity of 90%) and adding into 0.1mol/L sodium hydroxide solution, stirring and dissolving, filtering, adding 1mol/L hydrochloric acid solution into the filtrate to adjust pH to 2.0, precipitating for 48h, centrifuging and removing supernatant, adding 0.1mol/L hydrochloric acid solution for washing for three times, naturally precipitating and removing supernatant, and carrying out vacuum freeze drying for 48h to obtain purified humic acid (purity is close to 100%), and then passing the purified humic acid through a 600-mesh screen for later use.
(2) Preparation of humic acid complex ferrous ion solution
0.21g of purified humic acid was added to 100mL of 0.05mol/L FeSO4·7H2And (3) performing ultrasonic treatment on the O aqueous solution at room temperature for 30min, and then fully stirring the mixture for 12h at the rotation speed of 500 rpm.
(3) Preparation of nano zero-valent iron load material
With N2For protection, under the condition that the rotating speed is 500rpm, aerating for 30min, adding a reducing agent into the humic acid complex ferrous ion solution obtained in the step (2), and controlling the dropping speed to be 2mL/min, wherein the reducing agent is 0.2mol/L NaBH4Aqueous solution, reducing agent in molar ratio, BH4 -：FeSO4·7H2O is 4: 1; after the addition is finished, continuously controlling the rotating speed to be 500rpm, and stirring for 20min to obtain a black solution; and then sealing the black solution, putting the black solution into an anaerobic glove box, adsorbing and separating the black solution by using a magnet, washing the obtained precipitate by using oxygen-free deionized water for 3 times, and finally, carrying out vacuum freeze drying for 48 hours to obtain the nano zero-valent iron load material.
The nano zero-valent iron-supported material and the purified humic acid obtained above were measured using a scanning electron microscope (GeminiSEM 500 schottky field emission scanning electron microscope), and the results are shown in fig. 1. Fig. 1 is a scanning electron microscope image of purified humic acid and a nano zero-valent iron loaded material provided in embodiment 1 of the present invention, wherein, a and c are morphology images of the purified humic acid under different magnifications, and b and d are morphology images of the nano zero-valent iron loaded material under different magnifications. As can be seen from figure 1, the surface of humic acid is smooth and flat, after humic acid is taken as a carrier and loaded by nano zero-valent iron, a rough, uneven and compact zero-valent iron layer is formed on the surface of humic acid, and partial ferric oxide globules are formed on the surface of the zero-valent iron layer and connected with humic acid. The diameter of the nanometer zero-valent iron particles is about 0.1-1 nm, and the particle size distribution range of the external small balls is 50-70 nm.
Comparative example 1
The nanometer zero-valent iron particle is prepared through the following steps:
100mL of 0.05mol/L FeSO is prepared4·7H2O aqueous solution, with N2For protection, aerating at 500rpm for 30min, adding reducing agent into the aqueous solution, and controlling the dropping rate2mL/min, and the reducing agent is 0.2mol/L NaBH4Aqueous solution, reducing agent in molar ratio, BH4 -：FeSO4·7H2O is 4: 1; after the addition is finished, continuously controlling the rotating speed to be 500rpm, and stirring for 20min to obtain a black solution; and then sealing the black solution, putting the black solution into an anaerobic glove box, adsorbing and separating by using a magnet, washing the obtained precipitate for 3 times by using oxygen-free deionized water, and finally, carrying out vacuum freeze drying for 48 hours to obtain the nano zero-valent iron particles.
The nano zero-valent iron load material obtained in example 1 and the nano zero-valent iron particles described in comparative example 1 were measured by an X-ray diffractometer (smartlab multifunctional targeting X-ray diffractometer), and the results are shown in fig. 2, where fig. 2 is an X-ray diffraction pattern of the nano zero-valent iron particles and the nano zero-valent iron load material provided by the present invention. As can be seen from fig. 2, when the scanning angle 2Theta is 20-80 °, a distinct diffraction peak appears at 2 Theta-44.965 °, and the diffraction peak is found to correspond to the 110-plane diffraction (Fe-110) in the standard PDF card of the control iron, indicating that the supported nano zero-valent iron is successfully prepared in example 1. A diffraction peak for maghemite appears at 34.8 ° 2Theta, which is also present in the unloaded control zero-valent iron, probably due to oxidation by oxygen in the air during sample measurement.
Example 2
The method is used for investigating the removing effect of the nano zero-valent iron load material with different concentrations on the hexavalent chromium in the water body, and comprises the following specific steps:
to 50mL of a hexavalent chromium aqueous solution having a concentration of 25mg/L, pH ═ 5.0, 0.005g, 0.0125g, 0.025g, 0.0375g, 0.050g of the nano zero valent iron supporting material finally obtained in example 1 were added, and each addition amount was made in parallel. The reaction is carried out for 3 hours at normal temperature and normal pressure, a diphenylcarbonyldihydrazide spectrophotometric method is used in the reaction process, an ultraviolet spectrophotometer is adopted to measure the residual hexavalent chromium in the solution, then the concentration of the load-type nano zero-valent iron material is taken as a horizontal coordinate, the removing efficiency of the hexavalent chromium is taken as a vertical coordinate to carry out mapping, the removing condition of the hexavalent chromium in the hexavalent chromium water solution with the concentration of 25mg/L by the nano zero-valent iron load material obtained in the embodiment 1 along with the change of the amount of the nano zero-valent iron load material added into the reaction system is obtained, and the result is shown in figure 3. FIG. 3 is a graph showing the effect of different dosages of nano zero-valent iron loading material on removing hexavalent chromium according to the embodiment 2 of the present invention. It can be seen from fig. 3 that the removal efficiency of hexavalent chromium is positively correlated with the nano zero-valent iron load material added into the reaction system, when 0.005g, 0.0125g of nano zero-valent iron load material is added, the removal efficiency of hexavalent chromium is only 18.296% and 47.434%, when 0.025g of nano zero-valent iron load material is added, hexavalent chromium is completely removed, and the concentration of corresponding nano zero-valent iron load material is 0.5 g/L.
Example 3
The nano zero-valent iron load material obtained in the example 1 is used for absorbing and reducing hexavalent chromium in water to remove hexavalent chromium, and meanwhile, the purified humic acid obtained in the step (1) in the example 1 and the nano zero-valent iron obtained in the comparative example 1 are used as a contrast, and the steps are as follows:
to 8 parts of 50mL of an aqueous hexavalent chromium solution having a concentration of 25mg/L and a pH of 5.0, 0.025g of the nano zero-valent iron supporting material finally obtained in example 1 (H-nZVI), 0.025g of the purified Humic Acid (HA) obtained in step (1) in example 1, 0.025g of the nano zero-valent iron particles obtained in comparative example 1 (nZVI), 0.0107g of the purified humic acid, and 0.0143g of the mixture of nano zero-valent iron particles obtained in comparative example 1 (HA + nZVI) were added, respectively, and two experiments were performed in parallel for each group. The reaction is carried out for 3 hours at normal temperature and normal pressure, a diphenylcarbonyldihydrazide spectrophotometric method is used in the reaction process, an ultraviolet spectrophotometer is adopted to measure the residual hexavalent chromium in the solution, then the reaction time is taken as a horizontal coordinate, the removal efficiency of the hexavalent chromium is taken as a vertical coordinate to carry out mapping, the result is shown in figure 4, and figure 4 is a comparative curve chart of the removal effect of different materials on the hexavalent chromium provided by the embodiment 3 of the invention. As can be seen from fig. 4, the removal efficiency of the nano zero-valent iron load material on hexavalent chromium is the same as the removal efficiency of nano zero-valent iron particles with iron equivalent of 1.75 times, which is 1.78 times of the removal efficiency of nano zero-valent iron particles with the same iron equivalent on hexavalent chromium, and the unloaded HA HAs almost no removal capability on hexavalent chromium, which indicates that the removal efficiency of nano zero-valent iron is greatly improved after humic acid loading.
The material after the reaction was measured by a scanning electron microscope (GeminiSEM 500 schottky field emission scanning electron microscope), and the scanning electron micrograph thereof is shown in fig. 5. FIG. 5 is SEM pictures of nanometer zero-valent iron-loaded material after reaction with hexavalent chromium, provided by example 3 of the present invention, wherein the pictures a, b, c, d are scanning electron microscope pictures under different magnifications. As can be seen from FIG. 5, the iron after the reaction is coated on the surface of humic acid in the form of flake iron oxide, which provides a convenient condition for the separation of solid particles after the reaction is finished.
The reacted H-nZVI is subjected to surface scanning to obtain fig. 6, and fig. 6 is an X-ray Energy Dispersion Spectrum (EDS) of the nano zero-valent iron-loaded material reacted with hexavalent chromium provided in example 3 of the present invention. It can be seen from fig. 6 that the mass fraction of chromium existing on the surface after the reaction is 10.8%, and the chromium is uniformly distributed, which indicates that the nano zero-valent iron load material can well adsorb the chromium on the surface of the humic acid coated by the oxidized zero-valent iron.
Example 4
The nano zero-valent iron load material obtained in the example 1 is used for carrying out adsorption reduction on hexavalent chromium in water under different pH conditions to remove the hexavalent chromium, and the steps are as follows:
to 50mL of an aqueous solution of hexavalent chromium having a concentration of 25mg/L and a pH of 5.0, 6.5, 8.0, 10.0, 0.025g of the nano zero-valent iron supporting material finally obtained in example 1 was added, respectively, two in parallel per pH condition. The reaction is carried out for 3 hours at normal temperature and normal pressure, a diphenylcarbonyldihydrazide spectrophotometric method is used in the reaction process, an ultraviolet spectrophotometer is adopted to measure the residual hexavalent chromium in the solution, then the reaction time is taken as a horizontal coordinate, the removing efficiency of the hexavalent chromium is taken as a vertical coordinate to carry out mapping, the removing condition of the hexavalent chromium in the hexavalent chromium aqueous solution with the concentration of 25mg/L by the change of the nano zero-valent iron load material obtained in the embodiment 1 along with the time is obtained, the result is shown in figure 7, and figure 7 is a comparison curve chart of the removing effect of the nano zero-valent iron load material provided by the embodiment 4 of the invention on the hexavalent chromium under different pH conditions.
Experimental results show that the nano zero-valent iron load material can well remove hexavalent chromium under different pH conditions. Under the acidic condition that the pH value is 5.0, 84.82% of hexavalent chromium can be removed in 30min, and hexavalent chromium can be completely removed in 90 min; under the condition of neutral meta-acid with pH of 6.5, 97.5 percent of hexavalent chromium can be removed within 3 hours; in a slightly alkaline environment with the pH value of 8.0, 88.81% of hexavalent chromium can be removed within 3 hours, and 83.68% of hexavalent chromium can be removed under an alkaline condition with the pH value of 10.0. The nano zero-valent iron load material can adapt to acidic, neutral and alkaline conditions, and keeps higher removal efficiency under the alkaline condition. The content of dissolved organic matter was determined to be below 5mg C/L (TOC) at all pH conditions. And (2) measuring the total iron and the trivalent chromium in the system solution in the reaction process, wherein the content of the total iron is lower than the detection limit (0.01mg/L), the concentration of the trivalent chromium is not more than 3mg/L at the highest in the early stage of the reaction, and the concentration of the trivalent chromium is 0mg/L along with the continuous reaction, which shows that the nano zero-valent iron load material in the system can efficiently remove the hexavalent chromium without residue.
Example 5
Referring to the preparation steps of example 1, except that in the preparation of the humic acid complexing ferrous ion solution in the step (2), the mass of the purified humic acid is 0.07g, namely the mass ratio of the purified humic acid to the ferrous ion is 1:4, and the corresponding nano zero-valent iron load material is prepared.
Example 6
Referring to the preparation steps of example 1, except that in the preparation of the humic acid complexing ferrous ion solution in the step (2), the mass of the purified humic acid is 0.14g, namely the mass ratio of the purified humic acid to the ferrous ion is 1:2, and the corresponding nano zero-valent iron load material is prepared.
Example 7
Referring to the preparation steps of example 1, except that in the preparation of the humic acid complexing ferrous ion solution in the step (2), the mass of the purified humic acid is 0.28g, namely the mass ratio of the purified humic acid to the ferrous ion is 1:1, and the corresponding nano zero-valent iron load material is prepared.
Example 8
Referring to the preparation steps of example 1, except that in the preparation of the humic acid complexing ferrous ion solution in the step (2), the mass of the purified humic acid is 0.35g, namely the mass ratio of the purified humic acid to the ferrous ion is 5:4, and the corresponding nano zero-valent iron load material is prepared.
Example 9
Referring to the preparation steps of example 1, except that in the preparation of humic acid complexed ferrous ions in the step (2), the mass of purified humic acid is 0.56g, namely the mass ratio of purified humic acid to ferrous ions is 2:1, and the corresponding nano zero-valent iron load material is prepared.
Example 10
The nano zero-valent iron load materials obtained in the embodiments 1, 5, 6, 7, 8 and 9 are used for absorbing and reducing hexavalent chromium in water, and the nano zero-valent iron load materials with the same concentration of iron equivalent are used for removing the hexavalent chromium, and the steps are as follows:
the nano zero-valent iron supporting materials obtained in each example were added to 50mL of hexavalent chromium aqueous solution with a concentration of 25mg/L, pH-6.5, respectively, so that the concentrations of the nano zero-valent iron supporting materials in the reaction system were 0.4375g/L (example 1), 0.3125g/L (example 5), 0.375g/L (example 6), 0.5g/L (example 7), 0.5625g/L (example 8), and 0.75g/L (example 9), respectively, and each reaction condition was in parallel. The reaction is carried out for 3 hours at normal temperature and normal pressure, a diphenylcarbonyldihydrazide spectrophotometric method is used in the reaction process to determine the residual hexavalent chromium in the solution by adopting an ultraviolet spectrophotometer, then the concentration of the nano zero-valent iron load material is taken as a horizontal coordinate, and the removing efficiency of the hexavalent chromium is taken as a vertical coordinate to carry out mapping, so that the removing condition of the hexavalent chromium in the hexavalent chromium water solution with the concentration of 25mg/L by the nano zero-valent iron load material of the embodiment 1 and the embodiments 5 to 9 is obtained along with the change of the amount of the nano zero-valent iron load material added into the reaction system, and the result is shown in figure 8, which is a comparative curve chart of the removing effect of the hexavalent chromium by different nano zero-valent iron load materials provided by the embodiment 10 of the.
Example 11
A nanometer zero-valent iron load material takes humic acid as a carrier, nanometer zero-valent iron particles are loaded on the surface of the humic acid, and the preparation process specifically comprises the following steps:
(1) preparation of humic acid complex ferrous ion solution
0.42g of the fermented bean curd purified in step (1) of example 1 was addedThe clozoic acid is added to 200mL of 0.05mol/L FeSO4·7H2And (3) performing ultrasonic treatment for 60min at room temperature in the O aqueous solution, and then fully stirring for 12h, wherein the rotating speed is controlled to be 500 rpm.
(2) Preparation of nano zero-valent iron load material
With N2For protection, under the condition that the rotating speed is 500rpm, aerating for 30min, adding a reducing agent into the humic acid complex ferrous ion solution obtained in the step (1), controlling the dropping speed to be 2mL/min, wherein the concentration of the reducing agent is 0.2mol/LNaBH4100mL of aqueous solution; after the addition is finished, continuously controlling the rotating speed to be 500rpm, and stirring for 20min to obtain a black solution; and then sealing the black solution, putting the black solution into an anaerobic glove box, adsorbing and separating the black solution by using a magnet, washing the obtained precipitate by using oxygen-free deionized water for 3 times, and finally, carrying out vacuum freeze drying for 48 hours to obtain the nano zero-valent iron load material.
Example 12
A nanometer zero-valent iron load material takes humic acid as a carrier, nanometer zero-valent iron particles are loaded on the surface of the humic acid, and the preparation process specifically comprises the following steps:
(1) preparation of humic acid complex ferrous ion solution
0.21g of humic acid purified in step (1) of example 1 was added to 100mL of 0.05mol/L FeSO4·7H2And (3) performing ultrasonic treatment on the O aqueous solution at room temperature for 30min, and then fully stirring the mixture for 12h at the rotation speed of 500 rpm.
(2) Preparation of nano zero-valent iron load material
With N2For protection, under the condition that the rotating speed is 500rpm, aerating for 30min, adding a reducing agent into the humic acid complex ferrous ion solution obtained in the step (1), controlling the dropping speed to be 1mL/min, wherein the concentration of the reducing agent is 0.2mol/LNaBH4100mL of aqueous solution, adding NaBH in the process4The aqueous solution was placed in an ice bath until the sodium borohydride was added to the reaction system. After the addition is finished, continuously controlling the rotating speed to be 500rpm, and stirring for 20min to obtain a black solution; sealing the black solution, placing into an anaerobic glove box, separating by magnet adsorption, washing the obtained precipitate with oxygen-free deionized water for 3 times, vacuum freeze drying for 48 hr,and obtaining the nano zero-valent iron load material.
Example 13
A nanometer zero-valent iron load material takes humic acid as a carrier, nanometer zero-valent iron particles are loaded on the surface of the humic acid, and the preparation process specifically comprises the following steps:
(1) preparation of humic acid complex ferrous ion solution
0.21g of humic acid purified in step (1) of example 1 was added to 100mL of 0.05mol/L FeSO4·7H2And (3) carrying out ultrasonic treatment on the O aqueous solution at room temperature for 2 hours, and then fully stirring the O aqueous solution for 10.5 hours at the rotation speed of 500 rpm.
(2) Preparation of nano zero-valent iron load material
With N2For protection, under the condition that the rotating speed is 500rpm, aerating for 30min, adding a reducing agent into the humic acid complex ferrous ion solution obtained in the step (1), controlling the dropping speed to be 2mL/min, wherein the concentration of the reducing agent is 0.2mol/LNaBH4100mL of aqueous solution, adding NaBH in the process4The aqueous solution was placed in an ice bath until the sodium borohydride was added to the reaction system. After the addition is finished, continuously controlling the rotating speed to be 500rpm, and stirring for 20min to obtain a black solution; and then sealing the black solution, putting the black solution into an anaerobic glove box, adsorbing and separating the black solution by using a magnet, washing the obtained precipitate by using oxygen-free deionized water for 3 times, and finally, carrying out vacuum freeze drying for 48 hours to obtain the nano zero-valent iron load material.
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 (10)
1. A nano zero-valent iron load material comprises humic acid and nano zero-valent iron particles loaded on the surface of the humic acid.
2. The nano zero-valent iron support material of claim 1, wherein the nano zero-valent iron particles completely wrap the surface of the humic acid to form a zero-valent iron layer.
3. The nano zero-valent iron supporting material according to claim 1, wherein the diameter of the nano zero-valent iron particles is 0.1-1 nm.
4. A preparation method of a nano zero-valent iron load material comprises the following steps:
a) mixing water-soluble ferrous salt and humic acid in water to obtain a mixed solution;
b) and in the atmosphere of protective gas, mixing the mixed solution with a reducing agent for reaction to obtain the nano zero-valent iron load material.
5. The method according to claim 4, wherein the water-soluble ferrous salt in step a) comprises ferrous sulfate.
6. The preparation method according to claim 4, wherein in the step a), the mass ratio of the iron element to the humic acid in the water-soluble ferrous salt is 1: (0.2 to 3); the content of iron element in the water-soluble ferrous salt in water is 0.025-0.1 mol/L.
7. The method according to claim 4, wherein in step b), the reducing agent comprises sodium borohydride.
8. The preparation method according to claim 4, wherein in the step b), the temperature of the mixing reaction is 15-35 ℃; the mixing reaction time is 0.5-1.5 h.
9. The method according to claim 4, wherein step b) comprises in particular:
and stirring the mixed solution in a protective gas atmosphere, dropwise adding a reducing agent aqueous solution into the mixed solution, and continuously stirring for reaction after the dropwise adding is finished to obtain the nano zero-valent iron load material.
10. A method for purifying hexavalent chromium in sewage comprises the following steps:
adding the nano zero-valent iron load material of any one of claims 1 to 3 or the nano zero-valent iron load material prepared by the preparation method of any one of claims 4 to 9 into sewage containing hexavalent chromium, wherein the nano zero-valent iron load material removes the hexavalent chromium in the sewage to obtain purified water.
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