Phosphorus removal adsorbent and preparation method thereof
Technical Field
The invention relates to the technical field of sewage dephosphorization, in particular to a dephosphorization adsorbent and a preparation method thereof.
Background
At present, the eutrophication problem of natural water bodies such as rivers, lakes and the like is very common, and phosphate is a key nutrient element causing eutrophication. Therefore, removal of phosphate at too high a concentration in the water body is particularly critical.
For biological cells, phosphate is an important constituent of molecules in the cell, constituting the backbone of phospholipids, nucleotides, nucleic acids and coenzymes. Therefore, phosphate radical is a limiting nutrient element, and the excessive content of the phosphate radical in the water body can cause the mass propagation of algae and other organisms in the water body, thereby further causing a series of reactions such as the reduction of the dissolved oxygen of the water body, the death of aquatic organisms, the deterioration of odor of the water body and the like.
The prior method for removing phosphate radical in water body comprises biological phosphorus removal technology, physical and chemical phosphorus removal technology and the like. These methods have all been applied in the field of treatment of contaminated water bodies. Among the above methods, the adsorption method belonging to the field of physical and chemical phosphorus removal technology has attracted extensive attention due to its characteristics of low cost, high efficiency, capability of recovering phosphorus resources, and the like.
The development of efficient phosphorus removal agents is an urgent need. The metal-containing phosphorus removal agent has been the focus of research due to its high selectivity and high efficiency for removing phosphorus. In recent years, due to its optical, catalytic and antibacterial properties, nano titanium dioxide is widely used in the fields of catalysts, cosmetics, paints, sun cream, plastics and the like. In addition, titanium dioxide nanoparticles are also popular as an adsorbent material due to their small size, large specific surface area, high surface energy, and large proportion of surface atoms.
Patent specification CN108355619A discloses a nano-adsorbent material for removing water pollutants, which contains the following components: 30-40 parts of nano titanium dioxide, 30-40 parts of nano zinc oxide, 5-10 parts of starch, 8-25 parts of modified activated carbon, 1-8 parts of resin and 1-2 parts of chitosan. The preparation method of the nano-adsorption material is simple blending.
Patent specification with publication number CN108773870A discloses an activated carbon-based water purifying agent, which is prepared from the following materials in parts by weight: 80-150 parts of coconut peel, 20-40 parts of chitosan, 5-6 parts of chloroacetic acid, 30-60 parts of polyhydric alcohol, 5-10 parts of methacrylamide, 1-3 parts of initiator, 0.1-0.5 part of organosilicate, 10-30 parts of organic titanate, 2-6 parts of silane coupling agent and 50-60 parts of solvent. The activated carbon-based water purifying agent is compounded by porous carbon, grafted amphoteric chitosan and modified titanium dioxide, so that the water purifying agent integrates the functions of adsorption, flocculation, catalytic degradation and the like. However, the patent specification does not refer to the effect in terms of phosphorus removal.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a phosphorus removal adsorbent, which utilizes nano titanium dioxide to be loaded on an adsorbent based on activated carbon and chitosan, overcomes the defects of poor adsorption effect, insufficient strength of the common adsorbent, difficult removal, easy secondary pollution and the like of the common adsorbent, improves the adsorption capacity of the adsorbent, has low economic cost of selected materials, can efficiently adsorb phosphate ions in water, effectively improves the wastewater treatment capacity, and realizes the virtuous cycle of environment-economy.
A preparation method of a phosphorus removal adsorbent comprises the following steps:
(1) adding chitosan and activated carbon in a mass ratio of 1 (1-10) into an acetic acid solution to obtain a mixed solution;
(2) mixing a sodium hydroxide solution and absolute ethyl alcohol in a volume ratio of 1: (10-20) mixing to obtain a stationary liquid;
(3) dripping the mixed solution into the stationary liquid, washing and drying the precipitate to obtain a carrier adsorbent;
(4) adding nano titanium dioxide and a dispersing agent into water to obtain a dispersion liquid, adding a carrier adsorbent into the dispersion liquid for loading, filtering to obtain a solid, washing, drying, and roasting at 300-600 ℃ for 2-3 h to obtain the phosphorus removal adsorbent.
In the step (1), preferably, the mass ratio of the chitosan to the activated carbon is 1 (5-10), the activated carbon has a high ratio, and the adsorption effect is good.
The acetic acid solution has the function of providing an acid environment, preferably, the mass concentration of the acetic acid solution is 1% -8%, and the ratio of the mass of the acetic acid solution to the total mass of the chitosan and the activated carbon is (10-80): 1. the acetic acid solution is too much, and then more alkali is needed, which causes waste.
The mixed solution is thick.
In the step (2), the mixed solution of absolute ethyl alcohol and sodium hydroxide is an inorganic fixing agent.
The sodium hydroxide solution has the function of providing an alkaline environment, and preferably, the mass concentration of the sodium hydroxide solution is 25-45%.
The washing in the step (3) and the step (4) can adopt distilled water or deionized water, and the drying can adopt room-temperature air drying for 12-24 hours or drying in an oven at 105 ℃ for 2-4 hours.
In the step (4), the particle size of the nano titanium dioxide is preferably 50-80 nm, and the nano titanium dioxide has a good adsorption effect.
In order to achieve a better adsorption effect and minimize environmental hazards, the mass concentration of the nano titanium dioxide in the dispersion liquid is preferably 1-2%.
The concentration of the dispersing agent in the dispersion liquid can be 0.01-0.03 mg/L.
The dispersant may be sodium dodecylbenzene sulfonate.
In order to obtain better dispersion effect and loading effect, the mass ratio of the carrier adsorbent to the dispersion liquid is preferably 1: (10-30).
In order to accelerate the loading efficiency and improve the loading effect, the loading can be carried out by adopting a heating and stirring mode, the heating can be water bath heating, and the preferable heating temperature is 50-70 ℃. Preferably, the stirring time is 12-36 h, the length of the stirring time determines the length of the load reaction time, the stirring time is too short, the load is incomplete, and the stirring time is too long and is not necessary.
In the step (4), preferably, the pH value of the washed solid is 7-7.5, so as to ensure that impurities are washed cleanly.
Preferably, the roasting temperature is 350-450 ℃, and a good adsorption effect is maintained.
The invention also provides the phosphorus removal adsorbent prepared according to the preparation method of the phosphorus removal adsorbent.
The nano titanium dioxide is fixed on the surface of the carrier adsorbent, so that the adsorption capacity of the phosphorus removal adsorbent is improved, and the nano titanium dioxide is mainly fixed on the surface of the phosphorus removal adsorbent through chelation, covalent bonds or coordination bonds and phosphate radicals. The synergistic effect of the substances increases the dephosphorization effect of the dephosphorization adsorbent.
Compared with the prior art, the invention has the main advantages that: the phosphorus removal adsorbent overcomes the defects of poor adsorption effect of a common adsorbent, insufficient strength of the adsorbent, difficulty in removal, easiness in causing secondary pollution and the like, is simple and stable in preparation method, good in strength of the granular formed body, low in economic cost of the selected material, and capable of efficiently adsorbing phosphate ions in a water body, effectively improving the wastewater treatment capacity and realizing the virtuous cycle of environment-economy.
Drawings
FIG. 1 is a flow chart of the preparation of the phosphorus removal adsorbent of the present invention;
FIG. 2 shows the phosphorus removal efficiency of each of the carrier adsorbents and the phosphorus removal adsorbents of examples 1 to 3.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
(1) As shown in fig. 1A and 1B, 3g of the mixture was weighed to have a mass ratio of 1: 3, adding the mixture of chitosan and activated carbon into an acetic acid solution with the mass concentration of 1.2% to obtain a thick mixed solution;
(2) mixing a sodium hydroxide solution with a mass concentration of 40% and absolute ethyl alcohol in a volume ratio of 1: 10 mixing to obtain alkaline stationary liquid;
(3) as shown in fig. 1C, the mixed solution is added dropwise to 80mL of stationary liquid to obtain particle pellets, the particle pellets are washed to neutrality with distilled water, and dried to obtain a carrier adsorbent;
(4) as shown in fig. 1D, adding nano titanium dioxide and sodium dodecylbenzene sulfonate into water to obtain a dispersion solution, wherein the mass concentration of the nano titanium dioxide in the dispersion solution is 1%, and the concentration of the sodium dodecylbenzene sulfonate is 0.017mol/L, adding the carrier adsorbent into the dispersion solution, heating in a water bath at 60 ℃, maintaining magnetic stirring for 24 hours, and the rotating speed of magnetons is 300 rpm;
(5) as shown in fig. 1E and 1F, after stirring, filtering, washing with distilled water to neutrality, drying, calcining in a muffle furnace at 400 ℃ for 2h, and cooling to obtain the dephosphorizing adsorbent.
Example 2
(1) Weighing 3g of the following components in a mass ratio of 1: 5, adding the mixture of chitosan and activated carbon into an acetic acid solution with the mass concentration of 1.2% to obtain a thick mixed solution;
(2) mixing a sodium hydroxide solution with a mass concentration of 40% and absolute ethyl alcohol in a volume ratio of 1: 15 to obtain alkaline stationary liquid;
(3) dripping the mixed solution into 100mL of stationary liquid to obtain small particles, washing the small particles to be neutral by using distilled water, and drying to obtain a carrier adsorbent;
(4) adding nano titanium dioxide and sodium dodecyl benzene sulfonate into water to obtain a dispersion liquid, wherein the mass concentration of the nano titanium dioxide in the dispersion liquid is 2%, and the concentration of the sodium dodecyl benzene sulfonate is 0.03mol/L, adding a carrier adsorbent into the dispersion liquid, heating in a water bath at 50 ℃, and maintaining magnetic stirring for 12 hours, wherein the rotating speed of a magneton is 350 rpm;
(5) and filtering after stirring, washing the mixture to be neutral by using distilled water, drying the mixture, then putting the dried mixture into a muffle furnace, roasting the dried mixture for 2.5 hours at the temperature of 400 ℃, and cooling the dried mixture to obtain the phosphorus removal adsorbent.
Example 3
(1) Weighing 3g of the following components in a mass ratio of 1: 7, adding the mixture of chitosan and activated carbon into an acetic acid solution with the mass concentration of 1.2% to obtain a thick mixed solution;
(2) mixing a sodium hydroxide solution with a mass concentration of 40% and absolute ethyl alcohol in a volume ratio of 1: 20 to obtain alkaline stationary liquid;
(3) dripping the mixed solution into 110mL of stationary liquid to obtain small particles, washing the small particles to be neutral by using distilled water, and drying to obtain a carrier adsorbent;
(4) adding nano titanium dioxide and sodium dodecyl benzene sulfonate into water to obtain a dispersion liquid, wherein the mass concentration of the nano titanium dioxide in the dispersion liquid is 1.5%, and the concentration of the sodium dodecyl benzene sulfonate is 0.01mol/L, adding a carrier adsorbent into the dispersion liquid, heating in a water bath at 70 ℃, maintaining magnetic stirring for 36 hours, and keeping the rotating speed of magnetons at 400 rpm;
(5) and filtering after stirring, washing the mixture to be neutral by using distilled water, drying the mixture, then putting the dried mixture into a muffle furnace, roasting the dried mixture for 2 hours at 450 ℃, and cooling the roasted mixture to obtain the phosphorus removal adsorbent.
Application example
The phosphorus removal adsorbent obtained in example 1-3 was used as an experimental group, and the carrier adsorbent was used as a control group.
0.0325g of samples of the experimental group and the control group are respectively weighed and put into a centrifuge tube filled with potassium dihydrogen phosphate solution, and the phosphorus concentration in the potassium dihydrogen phosphate solution is 50 mg/L. Three replicates were set up for each sample.
The tube was placed in a constant temperature shaking chamber, shaken at 25 ℃ and 180rpm for 12 hours, and then centrifuged at 4 ℃ and 10000rpm for 5 minutes. The supernatant after the completion of the centrifugation was subjected to molybdate-based determination of the concentration of phosphorus in water, and the results are shown in FIG. 2.
It can be seen that the phosphorus removal efficiency of the phosphorus removal adsorbent of the experimental group is far higher than that of the carrier adsorbent of the control group, which indicates that the phosphorus removal adsorbent loaded with the nano titanium dioxide can efficiently adsorb phosphate ions in a water body, and the adsorption performance is remarkably improved.
The common adsorbent is poor in adsorption effect, insufficient in strength, easy to wear and drop powder, and further causes secondary pollution and the like due to the fact that the common adsorbent in the water body is not easy to remove. The phosphorus removal adsorbent provided by the invention is high in strength, is in a particle ball shape, is not easy to wear or drop powder, cannot cause secondary pollution, and the adopted raw materials cannot cause pollution, so that the wastewater treatment capacity can be effectively improved, and the environment-economy virtuous cycle is realized.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.