CN115591535B - 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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- CN115591535B CN115591535B CN202211395451.0A CN202211395451A CN115591535B CN 115591535 B CN115591535 B CN 115591535B CN 202211395451 A CN202211395451 A CN 202211395451A CN 115591535 B CN115591535 B CN 115591535B
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- 239000006260 foam Substances 0.000 title claims abstract description 81
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 63
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 62
- 239000010452 phosphate Substances 0.000 title claims abstract description 62
- 238000001179 sorption measurement Methods 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000001035 drying 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 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 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 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 235000011837 pasties Nutrition 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
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002360 preparation method Methods 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
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 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
- 238000004140 cleaning Methods 0.000 claims description 5
- 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 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 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
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 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
- 239000010865 sewage Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 238000012851 eutrophication Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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
-
- 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 water, and relates to the technical field of composite materials and wastewater treatment. The LDH/GO-melamine foam disclosed by the invention is prepared by repeatedly soaking cleaned melamine foam in graphene oxide solution, then growing magnesium aluminum iron ternary metal hydroxide in situ on the melamine foam under a hydrothermal condition, washing and drying to obtain the LDH/GO-melamine foam serving as a rag-type adsorbent, and applying the LDH/GO-melamine foam to adsorption removal of phosphate in water. The LDH/GO-melamine foam adsorbent provided by the invention has the advantages of strong phosphate adsorption effect, high adsorption rate and high efficiency, ensures that the phosphate concentration (less than or equal to 10 mg/L) in wastewater reaches the primary standard of the comprehensive wastewater discharge standard (GB 8978-1996) in a short time, and has wide application potential in the phosphate removal and standard discharge of 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 of the LDH/GO modified melamine foam in adsorbing and removing phosphate in water.
Background
With the rapid development of economy, a large amount of sewage discharge has become an environmental problem of worldwide concern. The enrichment of phosphorus in wastewater can lead to deterioration of the aquatic ecosystem and loss of water resource utilization. The phosphate compound can accumulate in the water body and reach the concentration threshold, and according to research, 0.02mg/L PO 4 3- Is sufficient to stimulate algae growth, resulting in eutrophication of the water body. Therefore, many countries impose strict phosphorus emission standards in sewage. In China, the discharge of phosphate in the effluent of sewage treatment plants needs to reach the first-level standard (0.5 mg/L). To cope with the implementation of high phosphorus emission standards, it is necessary to reduce the phosphate discharged into the water body, which presents new technical challenges for the dephosphorization of sewage treatment plants (WWTPs).
Currently, widely adopted dephosphorization processes include biological, chemical precipitation and physical methods, and intensified biological dephosphorization (EBPR) with low cost and high dephosphorization efficiency is generally preferred for large-scale sewage treatment plants. However, the process has strict requirements on water quality, and secondary pollution may be caused by extracting phosphorus resources from the residual sludge. Chemical precipitation is suitable for removing and recovering high concentrations of phosphate. However, too high a content of precipitates (e.g., iron and aluminum salts) increases the difficulty of desalting, and a large amount of the drug increases the treatment cost. The membrane separation technology, the electrochemical dephosphorization and the ion exchange method are difficult to widely popularize due to the problems of complex operation, high energy consumption, high cost and the like. The adsorption method can avoid the problems caused by the process, has the advantages of simple operation, economy, practicability, large capacity, rapid dephosphorization, recycling and the like, and is considered to be an excellent dephosphorization 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 material is loaded in the space with rich MF, so that the adsorption surface area can be effectively increased, and the problem of collecting and recycling the adsorbent is solved. In the environmental field, MF is often researched 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 prior modification methods have the problems of higher cost, foam slag falling and the like. The metal hydroxide (LDH) has the advantages of strong adsorption capacity, anion exchange property and the like due to the special layered structure, becomes a research hot spot 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 staff of the invention introduces metal hydroxide (LDH)/Graphene Oxide (GO) into the MF-rich space to prepare a new rag-type adsorbent, and the LDH/GO-MF can be taken out after being immersed in water to remove phosphate, and the phosphate concentration in the water body directly reaches the standard to be discharged, so that good economic and environmental benefits are generated.
Disclosure of Invention
Aiming at the problems that the low phosphate concentration removal effect in domestic sewage is difficult to reach the standard in a short time, the cost is high and the operation is complex, the invention provides the method for taking out the adsorbent after the adsorption is finished by taking the LDH/GO-melamine foam as the rag type adsorbent, so that the phosphate in the water body is simply and rapidly removed and reaches the phosphate discharge standard, and an economic and effective way is provided for removing the phosphate.
In order to achieve the aim of the invention, the invention provides an LDH/GO-melamine foam which is a rag type adsorbent prepared by modifying melamine foam with 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 melamine foam into small pieces, soaking with deionized water, cleaning, and drying.
S2, preparing graphene oxide:
s201, in an ice bath, mixing concentrated sulfuric acid and sodium nitrate in a proper proportion, and then gradually adding graphite powder and potassium permanganate in the stirring process, so as to always keep the mixed solution in the ice bath;
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, 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, carrying out violent reaction and heat release on the solution, after the solution is cooled to room temperature, adding 30wt% of hydrogen peroxide solution to remove redundant potassium permanganate in the mixed solution, reducing the high-valence manganese ions into divalent manganese ions, processing, changing the color of the mixed solution from brown to bright yellow, then washing with 5wt% of HCl solution to remove redundant manganese ions in the mixed solution, washing with deionized water to be neutral, and carrying out 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, stirring and ultrasonically dissolving uniformly to obtain a solution A.
S302, dispersing 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 equal amount of the solution A and the solution B, placing the mixture into a high-pressure reaction kettle of polytetrafluoroethylene, then placing the mixture into a forced air drying box for reacting for a period of time, and cooling the mixture to room temperature to obtain the mixture.
S304, repeatedly squeezing and soaking the melamine foam in the mixture for 3 times, washing with deionized water, and vacuum drying to obtain the required LDH/GO-melamine foam.
In the step S1, the melamine foam is cut into cubes with the length of 1 multiplied by 1cm, the soaking and cleaning temperature of deionized water is 80-90 ℃, the soaking and cleaning time is 12 hours, and the drying time is 6-12 hours.
Further, in the 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 stirring is continued for 12h after removing the ice bath.
Further, in the step S203, the ratio of the 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.
Further, in the step S3, the molar ratio of the magnesium sulfate, aluminum sulfate, and iron 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.
In step S3, the temperature of the 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 an 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 adsorb and remove phosphate in the water body.
Further, the specific method for removing phosphate in water by adsorbing the LDH/GO-melamine foam comprises the following steps:
adding LDH/GO-melamine foam into a phosphate water body, oscillating for 3-12 h in a constant-temperature oscillating box at the oscillating frequency of 180-200 rpm, taking a solution from the phosphate water body after a period of time, filtering, measuring the phosphate concentration until the phosphate concentration is not changed, and directly discharging the filtered aqueous solution after the adsorption balance is achieved, 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 adding amount of the LDH/GO-melamine foam is 4mg/mL, and the adsorption temperature is 25-30 ℃.
The invention has the following beneficial effects:
1. the LDH/GO-melamine foam adsorbent disclosed by the invention has a rich pore structure and a large specific surface area, and the melamine foam also provides more active sites for capturing phosphate ions in a solution. The traditional powder type adsorbent is changed, the foam type adsorbent can be used up and taken out, time and labor are saved, and the operation is simple and easy.
2. The LDH/GO-melamine foam adsorbent provided by the invention has higher phosphate removal efficiency, the removal rate in 5h can reach 95% under the conditions that the adsorption temperature is 30 ℃, the initial concentration of phosphate is 6-10 mg/L and the pH is about 7, the concentration of phosphate is lower than 0.5mg/L, and the phosphate meets the primary standard (0.5 mg/L) of the comprehensive sewage 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 in raw materials, easy to obtain, simple to prepare and low in cost, can obviously improve the treatment effect of phosphate, greatly shortens the time cost and has good economic and environmental benefits.
4. As the initial phosphate concentration increased from 6mg/L to 10mg/L, the adsorption amounts of example 1 and example 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 advantageous the adsorption of phosphate by the LDH/GO-melamine foam.
5. The adsorption rate of LDH/GO-melamine foam to phosphate is faster within 1h, and the adsorption rate gradually decreases after 1h until the adsorption equilibrium is reached. This is because the concentration of phosphate at the initial stage of adsorption is high, phosphate ions rapidly diffuse to the adsorption surface to bind to adsorption sites, the concentration of phosphate in the solution decreases with the lapse of time, the adsorption sites decrease, and the adsorption rate slows down until the adsorption equilibrium is reached.
Drawings
FIG. 1 is a physical view of an LDH/GO-melamine foam of example 1 of the present invention;
FIG. 2 is a physical view of the LDH/GO-melamine foam of example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of an LDH/GO-melamine foam of example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of an LDH/GO-melamine foam of example 2 of the present invention;
FIG. 5 is an X-ray diffraction pattern of the LDH/GO-melamine foam of examples 1 and 2 of the present invention;
FIG. 6 is a graph showing the dynamic effect of phosphate adsorption on LDH/GO-melamine foam prepared in example 1 of the present invention;
FIG. 7 is a graph showing the dynamic effect of phosphate adsorption on LDH/GO-melamine foam prepared in example 2 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
The cleaned melamine foam used in the examples of the present invention was: cutting melamine foam into cubes with the length 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: : 70mL of concentrated sulfuric acid and 2.0g of sodium nitrate are stirred and mixed in an ice bath, then 2g of graphite powder and 9g of potassium permanganate are gradually added in the continuous stirring process, and the ice bath is kept for 30min; removing ice bath, and stirring to obtain dark brown pasty material; and slowly adding 100mL of deionized water into the pasty mixture, reacting the solution vigorously and releasing heat, adding 5mL of 30wt% hydrogen peroxide after the solution is cooled to room temperature, fully mixing, washing with 5wt% HCl, washing with a large amount of deionized water to neutrality, and vacuum drying at 40 ℃ for 24 hours to obtain graphene oxide.
It is noted that the GO of the present invention can also be used directly with purchased products without limitation.
The LDH/GO-melamine foam provided by the embodiment of the invention is prepared by repeatedly soaking cleaned melamine foam in 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 serving as a rag-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 of MgSO 4 、0.11g Al 2 (SO 4 ) 3 ·18H 2 O、0.067g Fe 2 (SO 4 ) 3 And 0.33g of urea were stirred and dissolved ultrasonically uniformly, designated as solution A. Then 10mg of GO is dispersed in 50mL of deionized water, ultrasonic dispersion is carried out uniformly, 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 mixture is marked as solution B. Mixing the solution A and the solution B, stirring uniformly, transferring into a high-pressure reaction kettle of polytetrafluoroethylene, 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 squeezing and soaking melamine foam in the mixture for 3 times, washing with deionized water, and vacuum drying at 70 ℃ for 12 hours.
Example 2
The LDH/GO-melamine foam preparation method of this example 2 is the same as that of example 1, and specific steps are shown in example 1, except that the mass of GO in this example 2 is 5mg.
Application example 1
Dephosphorization adsorption tests are respectively carried out on the LDH/GO-melamine foam prepared in the examples 1 and 2 as an adsorption material, static adsorption experiments are carried out in a 50mL centrifuge tube, and water samples are taken after a period of time to test the phosphate concentration. Wherein the ratio 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 initial concentration of phosphate was 10mg/L under the same conditions as in application example 1.
Test data show that the adsorption materials obtained in the embodiments 1 and 2 of the invention have very remarkable removal efficiency (shown in table 1, fig. 6 and fig. 7) on phosphate in water, the removal rate of phosphate after adsorption equilibrium is as high as 95%, the concentration of phosphate in effluent reaches the first-stage sewage discharge standard, and the shortest adsorption equilibrium time is 2h, so that the treatment time is greatly shortened, and the cost is saved.
Table 1 phosphorus removal experiment results after adsorption equilibrium in different examples
The foregoing examples merely illustrate specific embodiments of the invention, which are described in greater detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, which are within the scope of the invention.
Claims (10)
1. An LDH/GO-melamine foam is characterized in that the LDH/GO-melamine foam is a rag-type adsorbent prepared by modifying melamine foam with ternary metal hydroxide and graphene oxide, wherein the ternary metal hydroxide is magnesium, aluminum and iron ternary metal hydroxide;
the preparation method of the LDH/GO-melamine foam specifically comprises the following steps:
s1, adding magnesium sulfate, aluminum sulfate, ferric sulfate and urea into a proper amount of deionized water, stirring, and carrying out ultrasonic dissolution to obtain a solution A;
s2, dispersing graphene oxide in a proper amount of deionized water, performing ultrasonic dissolution, and then adding melamine foam to obtain a solution B;
s3, mixing and stirring the solution A and the solution B, placing the mixture into a high-pressure reaction kettle of polytetrafluoroethylene, then placing the mixture into a blast drying box for reacting for a period of time, and cooling the mixture to room temperature to obtain a mixture;
s4, repeatedly squeezing and soaking the melamine foam in the mixture for 3 times, washing with deionized water, and vacuum drying to obtain the required LDH/GO-melamine foam.
2. The LDH/GO-melamine foam of claim 1, wherein the graphene oxide is prepared by a process comprising:
p1, in ice bath, mixing concentrated sulfuric acid and sodium nitrate in a proper proportion, and then gradually adding graphite powder and potassium permanganate in the stirring process, so as to always keep the mixed solution in the ice bath;
p2, removing the ice bath, and stirring to obtain a dark brown pasty mixture;
and P3, slowly adding deionized water into the pasty mixture, reacting the solution vigorously and releasing heat, adding 30wt% hydrogen peroxide solution after the solution is cooled to room temperature, fully mixing, washing with 5wt% HCl solution, washing with deionized water to be neutral, and drying in vacuum to obtain the graphene oxide.
3. The LDH/GO-melamine foam according to claim 1, wherein in step S1, the molar ratio of magnesium sulfate, aluminum sulfate, iron 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.
4. The LDH/GO-melamine foam according to claim 1, wherein in step S2, the melamine foam is subjected to a pretreatment method comprising: cutting melamine foam into cubes with the length of 1 multiplied by 1cm, soaking and cleaning with deionized water at 80-90 ℃ for 12 hours and drying for 6-12 hours.
5. The LDH/GO-melamine foam according to claim 1, wherein in step S3, the blow drying oven temperature is 120 ℃, the reaction time is 12 hours, the vacuum drying temperature is 70 to 80 ℃, and the vacuum drying time is 12 to 24 hours.
6. The LDH/GO-melamine foam according to claim 2, wherein in step P1, the ratio of sodium nitrate to 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 stirring is continued for 12h after removing the ice bath.
7. The LDH/GO-melamine foam according to claim 2, wherein in step P3, 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.
8. Use of an LDH/GO-melamine foam according to any one of claims 1 to 7, wherein the LDH/GO-melamine foam is added to a body of phosphate water to adsorb and remove phosphate from the body of water.
9. The use of LDH/GO-melamine foam according to claim 8, wherein the LDH/GO-melamine foam is adsorbed to remove phosphate from water by the specific method of:
adding LDH/GO-melamine foam into a phosphate water body, oscillating for 3-12 h in a constant-temperature oscillating box at the oscillating frequency of 180-200 rpm, taking a solution from the phosphate water body after a period of time, filtering, measuring the phosphate concentration until the phosphate concentration is not changed, and directly discharging the filtered aqueous solution after the adsorption balance is achieved, thereby achieving the purpose of removing phosphate in the water body.
10. The use of LDH/GO-melamine foam according to claim 9, wherein the initial concentration of phosphate in the phosphate body of water is 6-10 mg/L, the pH of the phosphate body of water is 4-10, and the volume of phosphate body of water is 25mL; the adding amount of the LDH/GO-melamine foam is 4mg/mL, and the adsorption temperature is 25-30 ℃.
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