CN115591535A - LDH/GO-melamine foam and application thereof in removing phosphate in water body - Google Patents
LDH/GO-melamine foam and application thereof in removing phosphate in water body Download PDFInfo
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- CN115591535A CN115591535A CN202211395451.0A CN202211395451A CN115591535A CN 115591535 A CN115591535 A CN 115591535A CN 202211395451 A CN202211395451 A CN 202211395451A CN 115591535 A CN115591535 A CN 115591535A
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- melamine foam
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- 239000006260 foam Substances 0.000 title claims abstract description 83
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 61
- 239000010452 phosphate Substances 0.000 title claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 11
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- -1 magnesium-aluminum-iron Chemical compound 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- 241000195493 Cryptophyta Species 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000011033 desalting Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009294 enhanced biological phosphorus removal Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses LDH/GO-melamine foam and application thereof in removing phosphate in a water body, and relates to the technical field of composite materials and wastewater treatment. The LDH/GO-melamine foam disclosed by the invention is characterized in that cleaned melamine foam is repeatedly soaked in a graphene oxide solution, then magnesium-aluminum-iron ternary metal hydroxide grows in situ in the melamine foam under a hydrothermal condition, and the LDH/GO-melamine foam is obtained after washing and drying and is used as a smeared adsorbent and applied to adsorption removal of phosphate in a water body. The LDH/GO-melamine foam adsorbent provided by the invention shows a strong phosphate adsorption effect, is high in adsorption rate and efficiency, enables the phosphate concentration (less than or equal to 10 mg/L) in the wastewater to reach the primary standard of the comprehensive wastewater discharge standard (GB 8978-1996) in a short time, and shows wide application potential in the removal and standard discharge of the phosphate in the wastewater.
Description
Technical Field
The invention relates to the technical field of composite materials and wastewater treatment, in particular to a preparation method of LDH/GO modified melamine foam and application thereof in adsorption removal of phosphate in water.
Background
With the rapid development of economy, the discharge of large amounts of sewage is an environmental concern worldwide. The enrichment of phosphorus in wastewater can lead to deterioration of aquatic ecosystems and loss of water resource utilization. The phosphate compound can be accumulated in the water body and reaches the concentration threshold, and researches show that 0.02mg/L PO 4 3- Can stimulate the growth of algae and cause eutrophication of water body. Therefore, many countries enforce strict phosphorus emission standards in wastewater. In China, the discharge of phosphate in the effluent of sewage treatment plants needs to reach the first-grade standard (0.5 mg/L). To meet the high phosphorus discharge standards, phosphate discharge into the water body must be reduced, which presents new technical challenges for phosphorus removal in sewage treatment plants (WWTPs).
At present, widely adopted phosphorus removal processes comprise a biological method, a chemical precipitation method and a physical method, and a large-scale sewage treatment plant usually selects Enhanced Biological Phosphorus Removal (EBPR) with low cost and high phosphorus removal efficiency. However, the process has severe requirements on water quality, and secondary pollution may be caused by extracting phosphorus resources from excess sludge. Chemical precipitation is suitable for removing and recovering phosphate with high concentration. However, the high content of precipitates (such as iron and aluminum salts) increases the difficulty of desalting, and the large amount of the agent increases the treatment cost. The membrane separation technology, the electrochemical phosphorus removal and the ion exchange method are difficult to be widely popularized due to the problems of complex operation, high energy consumption, high cost and the like. The adsorption method can avoid the problems generated by the process, has the advantages of simple operation, economy, practicability, large capacity, rapid phosphorus removal, recycling and the like, and is considered to be an excellent phosphorus removal technology.
Melamine Foam (MF) has a three-dimensional porous structure and excellent mechanical strength and elasticity, and is low in cost, light in weight, and high in porosity. Therefore, the adsorption surface area can be effectively increased by loading the adsorption material in the MF-rich space, and the problem of collecting and recycling the adsorbent is solved. In the environmental field, MF is often studied as a load framework to form a composite adsorbent material with a 3-dimensional structure and a large specific surface area, which is beneficial to the diffusion and absorption of gas or liquid pollutants, provides more adsorption active sites, and effectively improves the adsorption efficiency. However, most of the existing modification methods have the problems of high cost, foam slag removal and the like. Due to the special layered structure of the metal hydroxide (LDH), the metal hydroxide has the advantages of strong adsorption capacity, anion exchangeability and the like, and has been a research hotspot in the adsorption field, and the Graphene Oxide (GO) can promote the combination of MF and LDH due to the high chemical stability. Therefore, the technical personnel of the invention introduce metal hydroxide (LDH)/Graphene Oxide (GO) into the space rich in MF to prepare a novel wiping cloth type adsorbent, the LDH/GO-MF can be immersed into water to remove phosphate and then can be taken out, and the phosphate concentration in the water body directly reaches the standard and is discharged, thereby generating good economic and environmental benefits.
Disclosure of Invention
The invention aims to solve the problems that the low phosphate concentration in domestic sewage is difficult to reach the standard and discharge in a short time, the cost is high and the operation is complex, and provides a method for simply and quickly removing phosphate in a water body and reaching the phosphate discharge standard by taking LDH/GO-melamine foam as a 'wiped cloth type' adsorbent, wherein the adsorbent can be taken out after the adsorption is finished, so that an economic and effective way is provided for removing the phosphate.
In order to achieve the purpose of the invention, the invention provides LDH/GO-melamine foam which is a rag type adsorbent prepared by modifying modified melamine foam by using ternary metal hydroxide and graphene oxide, wherein the ternary metal hydroxide is magnesium, aluminum and iron ternary metal hydroxide.
The invention provides a preparation method of LDH/GO-melamine foam, which specifically comprises the following steps:
s1, pretreatment of melamine foam:
cutting the melamine foam into small pieces, soaking and cleaning the small pieces with deionized water, and drying the small pieces.
S2, preparing graphene oxide:
s201, mixing concentrated sulfuric acid and sodium nitrate in a proper proportion in an ice bath, then gradually adding graphite powder and potassium permanganate in the stirring process, and always keeping the mixed solution in the ice bath;
and S202, removing the ice bath, stirring, gradually increasing the temperature of the solution to normal temperature, gradually thickening the suspension in the process, gradually reducing the volume and continuously bubbling, and gradually reducing the amount of the mixed solution to form a dark brown pasty mixture.
S203, slowly adding deionized water into the pasty mixture, enabling the solution to react violently and release heat, after the solution is cooled to room temperature, adding a 30wt% hydrogen peroxide solution to remove redundant potassium permanganate in the mixed solution, reducing high-valence manganese ions into bivalent manganese ions, processing the bivalent manganese ions to change the color of the mixed solution from brown to bright yellow, then washing the mixed solution with 5wt% HCl solution to remove redundant manganese ions in the mixed solution, washing the mixed solution with deionized water to be neutral, and performing vacuum drying to obtain the graphene oxide.
S3, preparing LDH/GO-melamine foam:
s301, adding magnesium sulfate, aluminum sulfate, ferric sulfate and urea into a proper amount of deionized water, and stirring and ultrasonically dissolving uniformly to obtain a solution A.
S302, dispersing the graphene oxide prepared in the step S2 in a proper amount of deionized water, dissolving the graphene oxide in ultrasonic waves, and then adding the melamine foam prepared in the step S1 to obtain a solution B.
And S303, mixing and stirring the solution A and the solution B in equal amount, placing the mixture into a polytetrafluoroethylene high-pressure reaction kettle, then placing the kettle into an air-blowing drying oven for reaction for a period of time, and cooling the reaction product to room temperature to obtain a mixture.
S304, repeatedly extruding and soaking the melamine foam in the mixture for 3 times, cleaning with deionized water, and drying in vacuum to obtain the needed LDH/GO-melamine foam.
Further, in the step S1, the melamine foam is cut into cubes of 1 × 1 × 1cm, the soaking and cleaning temperature of the deionized water is 80-90 ℃, the soaking and cleaning time is 12 hours, and the drying time is 6-12 hours.
Further, in step S201, the ratio of the sodium nitrate to the concentrated sulfuric acid is (0.15 to 0.2): (6-7) g/ml;
the mass ratio of the sodium nitrate to the graphite powder to the potassium permanganate is 1:1:4.5, the ice bath time is 30min, and after the ice bath is removed, stirring is continuously carried out for 12h.
Further, in step S203, the ratio of the graphite powder to the deionized water added to the pasty mixture is (15-20): (1-1.5) g/L, wherein the ratio of the graphite powder to the 30wt% hydrogen peroxide solution is (0.3-0.4): (1-2) g/mL, the vacuum drying temperature is 40-50 ℃, and the vacuum drying time is 24h.
Further, in the step S3, the molar ratio of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is 6:1:1, the molar quantity of the urea is 3.3 times of the total metal ions of the magnesium sulfate, the aluminum sulfate and the ferric sulfate; the ratio of the graphene oxide to the melamine foam is (5-10): (0.3-0.6) mg/g; the ratio of the magnesium sulfate to the graphene oxide is (0.001-0.004): (5-10) mol/mg.
Further, in the step S3, the temperature of the forced air drying oven is 120 ℃, the reaction time is 12 hours, the vacuum drying temperature is 70-80 ℃, and the vacuum drying time is 12-24 hours.
The invention provides LDH/GO-melamine foam prepared by the preparation method of the LDH/GO-melamine foam.
The LDH/GO-melamine foam provided by the invention is added into a phosphate water body, and can remove phosphate in the water body by adsorption.
Further, the specific method for removing phosphate in water by LDH/GO-melamine foam adsorption comprises the following steps:
adding LDH/GO-melamine foam into a phosphate water body, oscillating for 3-12 h in a constant-temperature oscillation box with the oscillation frequency of 180-200 rpm, taking a solution from the phosphate water body after a period of time, measuring the phosphate concentration after filtering until the phosphate concentration does not change any more, and directly discharging the filtered water solution after achieving adsorption balance, thereby achieving the purpose of removing phosphate in the water body.
Further, in the phosphate water body, the initial concentration of phosphate is 6-10 mg/L, the pH value of the phosphate water body is 4-10, and the volume of the phosphate water body is 25mL; the addition amount of the LDH/GO-melamine foam is 4mg/mL, and the adsorption temperature is 25-30 ℃.
The invention achieves the following beneficial effects:
1. the LDH/GO-melamine foam adsorbent has a rich pore structure and a larger specific surface area, and the melamine foam also provides more active sites for capturing phosphate ions in the solution. The traditional powder type adsorbent is changed, the foam type adsorbent can be taken out after being used up, time and labor are saved, and the operation is simple and easy.
2. The LDH/GO-melamine foam adsorbent shows high phosphate removal efficiency, the removal rate can reach 95% within 5h of adsorption under the conditions that the adsorption temperature is 30 ℃, the initial concentration of phosphate is 6-10 mg/L and the pH value is about 7, the concentration of phosphate is lower than 0.5mg/L, and the LDH/GO-melamine foam adsorbent meets the primary standard (0.5 mg/L) of the integrated wastewater discharge standard (GB 8978-1996).
3. The adsorbent disclosed by the invention takes melamine foam as a substrate, takes magnesium sulfate, aluminum sulfate, ferric sulfate, graphene oxide and the like as doping materials, is wide and easy in raw material availability, simple to prepare and low in cost, can be used for remarkably improving the treatment effect of phosphate, greatly shortening the time cost and has good economic and environmental benefits.
4. As the initial phosphate concentration increased from 6mg/L to 10mg/L, the adsorbed amounts of examples 1 and 2 increased from 10.39mg/g and 13.49mg/g to 17.51mg/g and 24.25mg/g, respectively. The higher the initial concentration, the more favorable the LDH/GO-melamine foam is for adsorbing phosphate.
5. The LDH/GO-melamine foam has a higher adsorption rate on phosphate within 1h, and the adsorption rate is gradually reduced after 1h until the adsorption equilibrium is reached. This is because the phosphate concentration at the initial stage of adsorption is high, phosphate ions rapidly diffuse to the adsorption surface to bind to the adsorption sites, and as time passes, the concentration of phosphate in the solution decreases, the adsorption sites decrease, and the adsorption rate slows until the adsorption equilibrium is reached.
Drawings
FIG. 1 is a physical diagram of LDH/GO-melamine foam of example 1 of the present invention;
FIG. 2 is a physical diagram of LDH/GO-melamine foam of example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of LDH/GO-melamine foam of example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of LDH/GO-melamine foam of example 2 of the present invention;
FIG. 5 is an X-ray diffraction pattern of LDH/GO-melamine foams of examples 1 and 2 of the present invention;
FIG. 6 is a graph of the dynamic effect of LDH/GO-melamine foam adsorbing phosphate made in example 1 of the present invention;
FIG. 7 is a graph of the dynamic effect of LDH/GO-melamine foam made in example 2 of the present invention on phosphate adsorption.
Detailed Description
The following describes in detail specific embodiments of the present invention. All of the features disclosed in this specification, or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
The cleaned melamine foam used in the examples of the invention was: cutting the melamine foam into cubes of 1 multiplied by 1cm, soaking and cleaning with deionized water at the temperature of 80 ℃, for 12 hours, and drying for 12 hours to obtain the cleaned melamine foam.
The GO (graphene oxide) used in the embodiment of the invention is self-made, and the preparation method comprises the following steps: : stirring and mixing 70mL of concentrated sulfuric acid and 2.0g of sodium nitrate in an ice bath, then gradually adding 2g of graphite powder and 9g of potassium permanganate in the continuous stirring process, and keeping the ice bath for 30min; removing ice bath, and stirring to obtain dark brown paste; and slowly adding 100mL of deionized water into the pasty mixture, enabling the solution to react violently and release heat, cooling the solution to room temperature, adding 5mL of 30wt% hydrogen peroxide, fully mixing, washing by using 5wt% of HCl, washing by using a large amount of deionized water to be neutral, and drying in vacuum at 40 ℃ for 24 hours to obtain the graphene oxide.
It should be noted that GO in the present invention can also be directly used as a purchased product without limitation.
The LDH/GO-melamine foam disclosed by the embodiment of the invention is prepared by repeatedly soaking cleaned melamine foam in a graphene oxide solution, then growing magnesium-aluminum-iron ternary metal hydroxide (Mg/Al/Fe-LDH) in situ on the melamine foam under a hydrothermal condition, and washing and drying the melamine foam to obtain the LDH/GO-melamine foam as a 'wiping cloth type' adsorbent.
Example 1
The preparation method of the LDH/GO-melamine foam comprises the following steps:
to 50mL of deionized water was added 0.12g MgSO 4 、0.11g Al 2 (SO 4 ) 3 ·18H 2 O、0.067g Fe 2 (SO 4 ) 3 And 0.33g of urea are stirred and dissolved uniformly by ultrasonic waves, and the solution A is marked. And then 10mg of GO is dispersed in 50mL of deionized water, the mixture is uniformly dispersed by ultrasonic, then 0.5g of cleaned melamine foam is added, and the mixture is extruded and soaked in GO dispersion liquid for multiple times, and the solution B is marked. And mixing the solution A and the solution B, stirring uniformly, transferring into a polytetrafluoroethylene high-pressure reaction kettle, and placing into a forced air drying oven, wherein the reaction temperature is 120 ℃, and the reaction time is 12 hours. After the reaction is finished, naturally cooling to room temperature, repeatedly extruding and soaking the melamine foam in the mixture for 3 times, cleaning with deionized water, and vacuum-drying at 70 ℃ for 12 hours.
Example 2
The preparation method of the LDH/GO-melamine foam of this example 2 is the same as that in example 1, and please refer to example 1 for specific steps, except that the mass of GO in this example 2 is 5mg.
Application example 1
The LDH/GO-melamine foams prepared in the above examples 1 and 2 were used as adsorbing materials to perform a phosphorus removal adsorption test, respectively, static adsorption experiments were performed in a 50mL centrifuge tube, and water samples were taken at intervals to test the phosphate concentration. Wherein the proportion of the adsorbent to the phosphate water body is 4mg/mL, the initial concentration of the phosphate is 6mg/L, the adsorption time is 5h, the adsorption temperature is 30 ℃, and the oscillation speed is 180rpm.
Application example 2
The conditions were the same as in application example 1, and the initial concentration of phosphate was 8mg/L.
Application example 3
The conditions were the same as in application example 1, and the initial concentration of phosphate was 10mg/L.
Test data show that the adsorbing materials obtained in the embodiments 1 and 2 of the invention have very significant removal efficiency on phosphate in water (as shown in table 1, fig. 6 and fig. 7), the removal rate of phosphate after adsorption balance is as high as 95%, the concentration of phosphate in effluent reaches the first-level sewage discharge standard, the shortest adsorption balance time is 2h, the treatment time is greatly shortened, and the cost is saved.
TABLE 1 dephosphorization experiment results after adsorption equilibrium of different examples
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (11)
1. An LDH/GO-melamine foam is characterized in that the LDH/GO-melamine foam is a rag type adsorbent prepared by modifying modified melamine foam by adopting ternary metal hydroxide and graphene oxide, wherein the ternary metal hydroxide is magnesium, aluminum and iron ternary metal hydroxide.
2. A method for preparing LDH/GO-melamine foam according to claim 1, comprising the following steps:
s1, pretreatment of melamine foam:
cutting melamine foam into small pieces, soaking and cleaning the small pieces with deionized water, and drying the small pieces;
s2, preparing graphene oxide:
s201, mixing concentrated sulfuric acid and sodium nitrate in a proper proportion in an ice bath, then gradually adding graphite powder and potassium permanganate in the stirring process, and always keeping the mixed solution in the ice bath;
s202, removing the ice bath, and stirring into a dark brown pasty mixture;
s203, slowly adding deionized water into the pasty mixture, enabling the solution to react violently and release heat, after the solution is cooled to room temperature, adding 30wt% of hydrogen peroxide solution, fully mixing, washing with 5wt% of HCl solution, washing with deionized water until the solution is neutral, and drying in vacuum to obtain graphene oxide;
s3, preparing LDH/GO-melamine foam:
s301, adding magnesium sulfate, aluminum sulfate, ferric sulfate and urea into a proper amount of deionized water, and stirring and ultrasonically dissolving uniformly to obtain a solution A;
s302, dispersing the graphene oxide prepared in the step S2 in a proper amount of deionized water, performing ultrasonic dissolution, and then adding the melamine foam prepared in the step S1 to obtain a solution B;
s303, mixing and stirring the solution A and the solution B, placing the mixture into a polytetrafluoroethylene high-pressure reaction kettle, then placing the reaction kettle into an air-blast drying oven for reaction for a period of time, and cooling the reaction kettle to room temperature to obtain a mixture;
s304, repeatedly extruding and soaking the melamine foam in the mixture for 3 times, cleaning with deionized water, and drying in vacuum to obtain the needed LDH/GO-melamine foam.
3. A method for preparing LDH/GO-melamine foam according to claim 2, wherein in step S1, the melamine foam is cut into 1 × 1 × 1cm cubes, the deionized water soaking and cleaning temperature is 80-90 ℃, the soaking and cleaning time is 12h, and the drying time is 6-12 h.
4. A method for preparing LDH/GO-melamine foam according to claim 2, wherein in step S201, the ratio of the sodium nitrate to the concentrated sulfuric acid is (0.15-0.2): (6-7) g/ml;
the mass ratio of the sodium nitrate to the graphite powder to the potassium permanganate is 1:1:4.5, the ice bath time is 30min, and after the ice bath is removed, the stirring is continued for 12h.
5. A method for preparing LDH/GO-melamine foam according to claim 2, wherein in step S203, the ratio of graphite powder to deionized water added to the pasty mixture is (15-20): (1-1.5) g/L, wherein the ratio of the graphite powder to the 30wt% hydrogen peroxide solution is (0.3-0.4): (1-2) g/mL, the vacuum drying temperature is 40-50 ℃, and the vacuum drying time is 24h.
6. A method for preparing LDH/GO-melamine foam according to claim 2, wherein in step S3, the molar ratio of the magnesium sulfate, the aluminum sulfate and the iron sulfate is 6:1:1, wherein the molar weight of the urea is 3.3 times of the total metal ions of the magnesium sulfate, the aluminum sulfate and the ferric sulfate; the ratio of the graphene oxide to the melamine foam is (5-10): (0.3-0.6) mg/g; the ratio of the magnesium sulfate to the graphene oxide is (0.001-0.004): (5-10) mol/mg.
7. A method for preparing LDH/GO-melamine foam according to claim 2, wherein in step S3, the temperature of the forced air drying oven is 120 ℃, the reaction time is 12h, the vacuum drying temperature is 70-80 ℃, and the vacuum drying time is 12-24 h.
8. An LDH/GO-melamine foam produced by the method of preparing an LDH/GO-melamine foam as claimed in any one of claims 2 to 7.
9. Use of an LDH/GO-melamine foam according to any one of claims 1 or 8, wherein the LDH/GO-melamine foam is added to a body of phosphate water and the phosphate is removed from the body by adsorption.
10. The use of LDH/GO-melamine foam according to claim 9, wherein the specific method for removing phosphate in water by adsorption of LDH/GO-melamine foam is as follows:
adding LDH/GO-melamine foam into a phosphate water body, oscillating for 3-12 h in a constant-temperature oscillation box at an oscillation frequency of 180-200 rpm, taking a solution from the phosphate water body at intervals, measuring the phosphate concentration after filtering until the phosphate concentration is not changed, and directly discharging the filtered water solution after adsorption balance is achieved, thereby achieving the purpose of removing phosphate in the water body.
11. The use of an LDH/GO-melamine foam as claimed in claim 10, wherein the initial concentration of phosphate in the phosphate water is 6-10 mg/L, the pH of the phosphate water is 4-10, and the volume of the phosphate water is 25mL; the addition amount of the LDH/GO-melamine foam is 4mg/mL, and the adsorption temperature is 25-30 ℃.
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