CN111250032A - Preparation method and application of magnetic fly ash/molybdenum disulfide composite material - Google Patents
Preparation method and application of magnetic fly ash/molybdenum disulfide composite material Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 146
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229940107698 malachite green Drugs 0.000 claims abstract description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 27
- 239000011733 molybdenum Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 66
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 21
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 21
- 239000011609 ammonium molybdate Substances 0.000 claims description 21
- 229940010552 ammonium molybdate Drugs 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000004065 wastewater treatment Methods 0.000 claims description 10
- 239000010883 coal ash Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
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- 238000004140 cleaning Methods 0.000 claims description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 36
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
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- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
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- 239000012498 ultrapure water Substances 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
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Images
Classifications
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention belongs to the field of adsorption materials, and provides a preparation method and application of a magnetic fly ash/molybdenum disulfide composite material. The magnetic fly ash/molybdenum disulfide composite material is obtained by taking fly ash as a raw material, sequentially carrying out acidification and magnetization modification, and then reacting with a precursor solution containing molybdenum. The specific surface area of the composite material is increased, the adsorption active sites are increased, and the adsorption performance is enhanced. The adsorbent is used for adsorbing malachite green, and the highest adsorption rate reaches 97%. And the magnetic field is applied, so that the magnetic material can be conveniently and efficiently recovered from the solution and recycled after regeneration. Therefore, the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention is simple and feasible, the raw material source is rich, the reaction condition is mild, and the process parameters are easy to control. The industrial waste residue fly ash is utilized to the maximum extent, and the problem of low degradation efficiency of a single adsorbent is solved.
Description
Technical Field
The invention belongs to the field of adsorption materials, and particularly relates to a preparation method and application of a magnetic fly ash/molybdenum disulfide composite material.
Background
In recent years, the fuel industry has rapidly developed and has brought about highly polluted dye wastewater. The dye wastewater has stable structure and toxicity, is difficult to biodegrade, not only causes serious pollution to the environment, but also has carcinogenic effect on human beings and other animals, so the treatment of the dye wastewater is particularly important. The conventional treatment methods include a chemical coagulation method, an advanced oxidation method and the like. The chemical coagulation method has good effect, and is economical and environment-friendly. However, when the method is used for treating wastewater, a large amount of coagulant is required to be added, a large amount of sludge is generated, and the post-treatment is troublesome; the advanced oxidation method can degrade organic dye into small molecular substances, so that the wastewater is purified and the degradation speed is high. But has strict requirements on treatment equipment, large energy consumption, is not suitable for large-scale treatment and has certain limitation on application. The method widely applied at present is an adsorption method, a commonly used adsorption material is activated carbon, although the adsorption efficiency is high, the activated carbon is expensive, the regeneration cost is high, and the wide application of the activated carbon is greatly limited. Therefore, the development of a novel adsorbing material with low cost and high performance has important significance for the treatment of fuel wastewater.
The discharge amount of the fly ash is increased year by year along with the development of industries such as the power industry and the like, and the fly ash becomes one of industrial waste residues with larger discharge amount in China. A large amount of fly ash is discharged into the atmosphere, enters water and soil through movement such as sedimentation, causes serious pollution and also harms human health. The fly ash has larger specific surface area and reaction activity, can be used as a cheap adsorbent to be applied to the fields of flue gas treatment, wastewater treatment and the like, but has low adsorption performance.
The nano-sized molybdenum disulfide has huge specific surface area and good adsorption performance, and has important significance for treating organic wastewater. But the molybdenum disulfide after adsorbing the fuel is very difficult to separate from the waste water, and secondary pollution is probably caused.
Disclosure of Invention
The invention is carried out to solve the problems and aims to provide a preparation method and application of a magnetic fly ash/molybdenum disulfide composite material.
The invention provides a preparation method of a magnetic fly ash/molybdenum disulfide composite material, which is characterized by comprising the following steps: step 1, pretreating fly ash: mixing the coal ash and an acid solution in proportion, stirring, cleaning, filtering, and drying at 70-90 ℃ to obtain acidified coal ash; step 2, preparing magnetic fly ash: adding acidified fly ash into a mixed solution of ferrous sulfate and ferric trichloride, stirring, heating, adding a sodium hydroxide solution, adjusting the pH to 8-9, aging at a certain temperature, cooling, washing and drying a precipitate to obtain magnetic fly ash; step 3, preparing a precursor solution containing molybdenum: weighing ammonium molybdate and thiourea, placing the ammonium molybdate and the thiourea in water, stirring, slowly adding ammonia water, and continuing stirring for a period of time to obtain a precursor solution of molybdenum; step 4, preparing the magnetic fly ash/molybdenum disulfide composite material: and putting the precursor solution containing molybdenum into a reaction kettle, adding a certain mass of magnetic fly ash, and heating for reaction to obtain a black solid, namely the magnetic fly ash/molybdenum disulfide composite material.
In the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: in the step 1, the acid solution is 10% of HCl, and the solid-to-liquid ratio of the coal ash to the 10% of HCl is 1: 4(g: L).
In the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: in the step 2, the mass ratio of the ferrous sulfate to the ferric trichloride to the acidified fly ash is 1: 1: 0.5-1: 1: 1.
in the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: in the step 3, the mass ratio of ammonium molybdate to thiourea is 1: 2-1: 3.
in the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: wherein, the concentration of ammonia water is 25%, and the solid-to-liquid ratio of ammonium molybdate to ammonia water is 0.35: 2(g: L).
The invention also provides a magnetic fly ash/molybdenum disulfide composite material, which is prepared by the preparation method of the magnetic fly ash/molybdenum disulfide composite material.
The invention also provides application of the magnetic fly ash/molybdenum disulfide composite material in dye wastewater treatment.
In the application of the magnetic fly ash/molybdenum disulfide composite material in the aspect of dye wastewater treatment, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: wherein the dye wastewater is a malachite green solution.
In the application of the magnetic fly ash/molybdenum disulfide composite material in the aspect of dye wastewater treatment, the magnetic fly ash/molybdenum disulfide composite material also has the following characteristics: wherein the pH value of the malachite green solution is 5-9, the concentration is 5-150 mg/L, and the adding amount of the magnetic fly ash/molybdenum disulfide composite material in the malachite green solution is 0.01-2.00 g/L.
Action and Effect of the invention
According to the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention, fly ash is used as a raw material, and the magnetic fly ash/molybdenum disulfide composite material is obtained after acidification and magnetization modification are sequentially carried out on the fly ash and then the fly ash reacts with a precursor solution containing molybdenum. Compared with the raw material fly ash, the specific surface area of the composite material is increased, the adsorption active sites are increased, and the adsorption performance is enhanced. The specific surface area of the fly ash is 0.8157m2Per gram, and the specific surface area of the magnetic fly ash/molybdenum disulfide is 45.7169m2(ii) in terms of/g. Therefore, when the adsorbent is used for adsorbing malachite green from a solution, the adsorption efficiency is greatly improved compared with that of the fly ash and molybdenum disulfide, and the highest adsorption rate reaches 97%. And the magnetic field is applied, so that the magnetic material can be conveniently and efficiently recovered from the solution and recycled after regeneration.
Therefore, the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the invention is simple and feasible, the raw material source is rich, the reaction condition is mild, and the process parameters are easy to control. The industrial waste residue fly ash is utilized to the maximum extent, the adsorption performance of the magnetic fly ash/molybdenum disulfide composite material is kept, the problem of low wastewater treatment efficiency of the fly ash is solved, and the problem of low degradation efficiency of a single adsorbent is solved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a magnetic fly ash/molybdenum disulfide composite in example 1 of the invention;
FIG. 2 is a graph showing the effect of adsorption performance in application example 1 of the present invention;
FIG. 3 is a graph showing the effect of adsorption performance in application example 2 of the present invention; and
fig. 4 is a graph showing the effect of adsorption performance in application example 3 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the preparation method and the application of the magnetic fly ash/molybdenum disulfide composite material of the invention are specifically described below with reference to the embodiment and the accompanying drawings.
The raw materials and reagents used in the following examples can be purchased from conventional commercial sources unless otherwise specified.
The invention provides a preparation method of a magnetic fly ash/molybdenum disulfide composite material, which comprises the following steps:
step 4, preparing the magnetic fly ash/molybdenum disulfide composite material: and putting the precursor solution containing molybdenum into a reaction kettle, adding a certain mass of magnetic fly ash, and heating for reaction to obtain a black solid, namely the magnetic fly ash/molybdenum disulfide composite material.
The specific operation of the step 1 is as follows: the raw material fly ash is firstly screened (100 meshes) to remove larger particle impurities, and the fly ash and 10% HCl are mixed according to the weight ratio of 1: 4(g: L), placing the mixed solution on a magnetic stirrer at a constant temperature (20 ℃) to stir for 1h, cooling to room temperature, washing with water, filtering, drying at 80 ℃ for 3h, and drying to obtain the acidified fly ash.
The specific operation of the step 2 is as follows: dissolving ferrous sulfate and ferric trichloride in ultrapure water, adding the acidified fly ash obtained in the step 1 after complete dissolution, stirring for 30min, heating the solution to 70 ℃, and adding a NaOH solution while quickly stirring to adjust the pH value to 8-9. And putting the mixed solution into a water bath kettle, aging for 4h at 100 ℃, then cooling to room temperature, repeatedly washing the precipitate with ultrapure water, putting the precipitate into a forced air drying oven, drying for 4h at 105 ℃, and sieving (100 meshes) to obtain the magnetic fly ash. Wherein the mass ratio of the ferrous sulfate to the ferric trichloride to the acidified fly ash is 1: 1: 0.5-1: 1:1, the concentration of the NaOH solution is 5 mol/L.
The method for testing the content of the molybdenum disulfide in the precursor solution containing molybdenum comprises the following steps: taking a certain volume of precursor solution containing molybdenum, putting the precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, and putting the reaction kettle into a drying box at 200 ℃ for reaction for 24 hours. And after the reaction is finished, repeatedly washing and centrifuging the obtained black solid, drying at 80 ℃ to obtain black molybdenum disulfide particles, and calculating to obtain the content of molybdenum disulfide in the black molybdenum disulfide particles.
The specific operation of the step 4 is as follows: and (3) putting the molybdenum-containing precursor solution obtained in the step (3) into a reaction kettle with a polytetrafluoroethylene inner container, adding the magnetic fly ash obtained in the step (2), and putting the mixture into a drying oven at 200 ℃ for reaction for 24 hours. And after the reaction is finished, repeatedly washing and centrifuging the obtained black solid, and drying at 80 ℃ to obtain the magnetic fly ash/molybdenum disulfide composite material. The mass ratio of the molybdenum disulfide to the magnetic fly ash is as follows: 2:1, 1:3, 1: 5.
The prepared magnetic fly ash/molybdenum disulfide composite material is applied to the aspect of dye wastewater treatment. The dye wastewater is a malachite green solution, the pH of the malachite green solution is 5-9, the concentration of the malachite green solution is 5-150 mg/L, and the adding amount of the magnetic fly ash/molybdenum disulfide composite material in the malachite green solution is 0.00-2.00 g/L.
< example 1>
In this embodiment, the mass ratio of the molybdenum disulfide to the magnetic fly ash is 2:1 of the magnetic fly ash/molybdenum disulfide composite material.
And step 3, weighing 0.70g of ammonium molybdate and 3.66g of thiourea, placing the ammonium molybdate and the thiourea in 30mL of high-purity water, magnetically stirring for 10 minutes, slowly adding 4mL of 25% ammonia water, and continuing stirring for 1 hour to obtain a precursor solution containing molybdenum.
The method comprises the following steps of: putting the obtained precursor solution containing molybdenum into a reaction kettle with a polytetrafluoroethylene inner container, and putting the reaction kettle into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, obtaining black solid, repeatedly washing and centrifuging, drying at 80 ℃ to obtain black molybdenum disulfide particles, and weighing the black molybdenum disulfide particles to be 0.062 g.
And 4, putting 30mL of the molybdenum-containing precursor solution obtained in the step 3 into a 50mL reaction kettle with a polytetrafluoroethylene inner container, adding 0.30g of magnetic fly ash, and putting the mixture into a drying oven at 200 ℃ for reaction for 24 hours. After the reaction is finished, repeatedly washing and centrifuging the obtained black solid, and drying at 80 ℃ to obtain the magnetic fly ash/molybdenum disulfide composite material, which is recorded as: the mass ratio of the molybdenum disulfide to the magnetic fly ash is 2:1 of the magnetic fly ash/molybdenum disulfide composite material.
Scanning electron microscope detection is carried out on the obtained magnetic fly ash/molybdenum disulfide composite material, and the result is shown in figure 1.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the magnetic fly ash/molybdenum disulfide composite material in example 1 of the present invention.
As can be seen from FIG. 1, the surface of the material is uneven and has a flower cluster shape, which is more favorable for adsorption.
< example 2>
In this embodiment, the mass ratio of the molybdenum disulfide to the magnetic fly ash prepared by the method is 1:1 of the magnetic fly ash/molybdenum disulfide composite material. Step 1 and step 2 are the same as in embodiment 1 and will not be described again.
And 3, weighing 0.35g of ammonium molybdate and 1.83g of thiourea, placing the ammonium molybdate and the thiourea in 30mL of high-purity water, magnetically stirring for 10 minutes, slowly adding 2mL of 25% ammonia water, and continuing stirring for 1 hour to obtain a precursor solution containing molybdenum.
The method comprises the following steps of: putting the precursor solution containing molybdenum into a reaction kettle with a polytetrafluoroethylene inner container, and putting the reaction kettle into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, obtaining black solid, repeatedly washing and centrifuging, drying at 80 ℃ to obtain black molybdenum disulfide particles, and weighing the black molybdenum disulfide particles to be 0.0306 g.
And 4, putting 30mL of the precursor solution containing molybdenum into a 50mL reaction kettle with a polytetrafluoroethylene inner container, adding 0.30g of magnetic fly ash, and putting the mixture into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, repeatedly washing and centrifuging the obtained black solid, and drying at 80 ℃ to obtain the magnetic fly ash/molybdenum disulfide composite material, which is recorded as: the mass ratio of the molybdenum disulfide to the magnetic fly ash is 1: 1.
< example 3>
In this embodiment, the mass ratio of the molybdenum disulfide to the magnetic fly ash prepared by the method is 1:3, the magnetic fly ash/molybdenum disulfide composite material. Step 1 and step 2 are the same as in embodiment 1 and will not be described again.
And 3, weighing 0.35g of ammonium molybdate and 1.83g of thiourea, placing the ammonium molybdate and the thiourea in 30mL of high-purity water, magnetically stirring for 10 minutes, slowly adding 2mL of 25% ammonia water, and continuing stirring for 1 hour to obtain a precursor solution containing molybdenum.
The method comprises the following steps of: putting the precursor solution containing molybdenum into a reaction kettle with a polytetrafluoroethylene inner container, and putting the reaction kettle into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, obtaining black solid, repeatedly washing and centrifuging, drying at 80 ℃ to obtain black molybdenum disulfide particles, and weighing the black molybdenum disulfide particles to be 0.0315 g.
And 4, putting 10mL of the precursor solution containing molybdenum into a 50mL reaction kettle with a polytetrafluoroethylene inner container, adding 0.30g of magnetic fly ash, and putting the mixture into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, repeatedly washing and centrifuging the obtained black solid, and drying at 80 ℃ to obtain the magnetic fly ash/molybdenum disulfide composite material, which is recorded as: the mass ratio of the molybdenum disulfide to the magnetic fly ash is 1: 3.
< example 4>
In this embodiment, the mass ratio of the molybdenum disulfide to the magnetic fly ash prepared by the method is 1:5 of the magnetic fly ash/molybdenum disulfide composite material. Step 1, step 2 and step 3 are the same as embodiment 2 and will not be described again.
And 4, putting 10mL of the precursor solution containing molybdenum into a 50mL reaction kettle with a polytetrafluoroethylene inner container, adding 0.50g of magnetic fly ash, and putting the mixture into a drying box at 200 ℃ for reaction for 24 hours. After the reaction is finished, repeatedly washing and centrifuging the obtained black solid, and drying at 80 ℃ to obtain the magnetic fly ash/molybdenum disulfide composite material, which is recorded as: the mass ratio of the molybdenum disulfide to the magnetic fly ash is 1:5 of the magnetic fly ash/molybdenum disulfide composite material.
< application example 1>
The magnetic fly ash/molybdenum disulfide composite materials prepared in examples 1-4 are respectively added into a malachite green solution for adsorbing malachite green.
The resulting solution was added to 20mL of 20mg/L malachite green solution at room temperature in an amount of 1g/L, and after adsorption in the dark for 40min, the absorbance was measured at λ 618nm using an ultraviolet-visible spectrophotometer. The test results are shown in FIG. 2.
As can be seen from fig. 2, the adsorption rates of the original fly ash and pure molybdenum disulfide particles to the malachite green solution are only 28.71% and 51.21%. Because the specific surface area of the fly ash is 0.8157m2Per gram, and the specific surface area of the magnetic fly ash/molybdenum disulfide is 45.7169m2(ii) in terms of/g. The specific surface area of the material is increased, the adsorption active sites are increased, and the adsorption performance is enhanced. And when the mass ratio of the molybdenum disulfide to the magnetic fly ash is 2: the composite material has the best removal efficiency of malachite green at 1 hour, and the removal efficiency reaches about 97 percent.
The specific surface area of the fly ash and the specific surface area of the magnetic fly ash/molybdenum disulfide are measured by a full-automatic rapid specific surface and porosity analyzer, and the types are as follows: ASAP2020, manufacturer: Mac instruments USA. 0.2g of a sample was weighed and subjected to a nitrogen adsorption and desorption experiment.
< application example 2>
5 portions of 20mL malachite green solution with a concentration of 20mg/L were prepared, and the pH was set to 5, 6, 7, 8, and 9 in this order. The magnetic fly ash/molybdenum disulfide composite material prepared in example 1 is added into the above malachite green solution according to the addition amount of 1g/L, and after adsorption for 40min in a dark state, the absorbance of the composite material is measured at a position where lambda is 618nm by using an ultraviolet-visible spectrophotometer. The test results are shown in FIG. 3.
Fig. 3 is a graph showing the effect of adsorption performance in application example 2 of the present invention.
As can be seen from fig. 3, the pH of the solution has a certain effect on the adsorption effect, and when the pH is 5, the removal rate of the composite material on the malachite green is better.
< application example 3>
200mL of 9 parts of malachite green solution with pH 5 are prepared, with the initial concentrations being in order: 5mg/L, 10mg/L, 15mg/L, 20mg/L, 40mg/L, 60mg/L, 90mg/L, 120mg/L, 150 mg/L. The magnetic fly ash/molybdenum disulfide composite material prepared in example 1 is added into the above malachite green solution according to the addition amount of 1g/L, and after adsorption for 40min in a dark state, the absorbance of the composite material is measured at a position where lambda is 618nm by using an ultraviolet-visible spectrophotometer. The test results are shown in FIG. 4.
Fig. 4 is a graph showing the effect of adsorption performance in application example 3 of the present invention.
As can be seen from fig. 4, the concentration of the malachite green solution is different, the influence on the adsorption performance of the material is different, and the removal rate of the composite material on the malachite green is better when the concentration is 150mg/L, that is, about 50mg of malachite green can be adsorbed per gram of the composite material.
Effects and effects of the embodiments
According to the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the embodiment of the invention, the fly ash is used as a raw material, and the magnetic fly ash/molybdenum disulfide composite material is obtained by sequentially carrying out acidification and magnetization modification on the fly ash and then reacting the fly ash with a precursor solution containing molybdenum. Compared with the raw material fly ash, the specific surface area of the composite material is increased, the adsorption active sites are increased, and the adsorption performance is enhanced. The specific surface area of the fly ash is 0.8157m2Per gram, and the specific surface area of the magnetic fly ash/molybdenum disulfide is 45.7169m2(ii) in terms of/g. Therefore, the adsorption efficiency is greatly improved compared with that of the fly ash and the molybdenum disulfide. For example, in application example 1, the adsorption rates of the original fly ash and pure molybdenum disulfide particles to the malachite green solution are only 28.71% and 51.21%, and the adsorption rate of the magnetic fly ash/molybdenum disulfide is up to 97%. And the magnetic field is applied, so that the magnetic material can be conveniently and efficiently recovered from the solution and recycled after regeneration.
Therefore, the preparation method of the magnetic fly ash/molybdenum disulfide composite material provided by the embodiment of the invention is simple and feasible, the raw material source is rich, the reaction condition is mild, and the process parameters are easy to control. The industrial waste residue fly ash is utilized to the maximum extent, the adsorption performance of the magnetic fly ash/molybdenum disulfide composite material is kept, the problem of low wastewater treatment efficiency of the fly ash is solved, and the problem of low degradation efficiency of a single adsorbent is solved.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The preparation method of the magnetic fly ash/molybdenum disulfide composite material is characterized by comprising the following steps:
step 1, pretreating fly ash: mixing the coal ash and an acid solution in proportion, stirring, cleaning, filtering, and drying at 70-90 ℃ to obtain acidified coal ash;
step 2, preparing magnetic fly ash: adding the acidified fly ash into a mixed solution of ferrous sulfate and ferric trichloride, stirring, heating, adding a sodium hydroxide solution, adjusting the pH value to 8-9, aging at a certain temperature, cooling, washing and drying a precipitate to obtain the magnetic fly ash;
step 3, preparing a precursor solution containing molybdenum: weighing ammonium molybdate and thiourea, placing the ammonium molybdate and the thiourea in water, stirring, slowly adding ammonia water, and continuing stirring for a period of time to obtain a precursor solution of the molybdenum;
step 4, preparing the magnetic fly ash/molybdenum disulfide composite material: and putting the precursor solution containing molybdenum into a reaction kettle, adding a certain mass of the magnetic fly ash, and heating for reaction to obtain a black solid, namely the magnetic fly ash/molybdenum disulfide composite material.
2. The method for preparing a magnetic fly ash/molybdenum disulfide composite material according to claim 1, wherein:
in step 1, the acid solution is 10% HCl, and the solid-to-liquid ratio of the coal ash to the 10% HCl is 1: 4(g: L).
3. The method for preparing a magnetic fly ash/molybdenum disulfide composite material according to claim 1, wherein:
in the step 2, the mass ratio of the ferrous sulfate to the ferric trichloride to the acidified fly ash is 1: 1: 0.5-1: 1: 1.
4. the method for preparing a magnetic fly ash/molybdenum disulfide composite material according to claim 1, wherein:
in step 3, the mass ratio of ammonium molybdate to thiourea is 1: 2-1: 3.
5. the method for preparing a magnetic fly ash/molybdenum disulfide composite material according to claim 1, wherein:
in step 4, the concentration of the ammonia water is 25%, and the solid-to-liquid ratio of the ammonium molybdate to the ammonia water is 0.35: 2(g: L).
6. The magnetic fly ash/molybdenum disulfide composite material is characterized by being prepared according to the preparation method of the magnetic fly ash/molybdenum disulfide composite material as claimed in any one of claims 1-5.
7. The application of the magnetic fly ash/molybdenum disulfide composite material in the aspect of dye wastewater treatment is characterized in that the magnetic fly ash/molybdenum disulfide composite material is the magnetic fly ash/molybdenum disulfide composite material in claim 6.
8. The use of the magnetic fly ash/molybdenum disulfide composite material as claimed in claim 7 in dye wastewater treatment, wherein:
wherein the dye wastewater is a malachite green solution.
9. The use of the magnetic fly ash/molybdenum disulfide composite material as claimed in claim 7 in dye wastewater treatment, wherein:
the pH value of the malachite green solution is 5-9, the concentration of the malachite green solution is 5-150 mg/L, and the adding amount of the magnetic fly ash/molybdenum disulfide composite material in the malachite green solution is 0.01-2.00 g/L.
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