A method for treating organic dye wastewater

Abstract

The present invention relates to the field of organic wastewater treatment, and particularly to a method for treating organic dye wastewater, using hypercrosslinked polyaniline (PS-HCPs) as an adsorbent to adsorb organic dyes in the wastewater. For the adsorbent of the present invention, octavinylsilsesquioxane with more functional groups and higher reaction activity is selected as the crosslinking agent to prepare a hybrid hypercrosslinked polyaniline with a high specific surface area, so as to improve the adsorption rate and adsorption capacity of organic dyes in water. The adsorbent has a high crosslinking density, making the adsorbent microscopically present a crosslinked network structure, which is convenient for dye molecules to enter the crosslinked network structure for adsorption. At the same time, the number of micropores and mesopores inside the adsorbent is ensured, which is not only conducive to the infiltration of dye molecules, but also can effectively capture the dye molecules, thereby doubling the adsorption rate and adsorption capacity of the dye molecules.

Description

Technical Field

[0001] The present invention belongs to the field of organic wastewater treatment, and particularly relates to a method for treating organic dye wastewater. Background Art

[0002] With the rapid development of industries such as chemical raw materials, medicine, packaging, printing, household, electronic communication, metal manufacturing, food processing, rubber and plastics, electrical machinery and equipment, etc., and the continuous acceleration of the urbanization process, a large amount of waste gas, wastewater and solid waste are generated. These toxic and harmful substances are wantonly discharged into the natural environment, causing serious pollution problems in the atmosphere, soil and water bodies on which humans depend for survival. Benzene and its derivatives are important air and water pollutants. Such substances can cause great harm to the human hematopoietic function and are carcinogenic substances, seriously affecting human health and life. Therefore, in order to solve the current multi-faceted survival crisis of mankind, improve people's living environment, and improve the quality of human life, removing these pollutants is one of the most urgent tasks currently faced by mankind.

[0003] Currently, experts and scholars from various countries have conducted a large number of experimental studies on removing pollutants such as benzene and its derivatives from the ecological environment. In the experimental studies, the methods mainly used include catalytic combustion method, condensation method, membrane separation method, adsorption method, photodegradation method, etc. Compared with the catalytic combustion method, photodegradation method and membrane separation method, the adsorption method has the advantages of simple operation, simple experimental equipment, low energy consumption, high economic benefits, etc., and is also a hot topic that has been studied and discussed in recent years. The adsorbents currently used mainly include activated carbon and modified activated carbon series adsorbents, zeolite molecular sieve adsorbents, graphene adsorbents, hypercrosslinked polymers, organic framework polymers, etc.

[0004] Hypercrosslinked polyaniline (HCPANI) is a new type of organic microporous material with a highly crosslinked structure. Since American scientist Frantisek Svec prepared hypercrosslinked polyaniline in 2007, due to the large number of microporous structures and N heteroatoms in hypercrosslinked polyaniline, and its good performance in applications such as H2 and CO2 adsorption and storage, supercapacitors, etc., it has received great attention from the majority of scientific and technological workers and is a research hotspot in the current new material field. However, the existing methods for preparing hypercrosslinked polyaniline have deficiencies such as harsh reaction conditions and high synthesis costs, and the removal effect on organic pollutants in water is not good. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a method for treating organic dye wastewater.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for treating organic dye wastewater, characterized in that hypercrosslinked polyaniline (PS-HCPs) is used as an adsorbent to adsorb organic dyes in the wastewater.

[0008] Preferably, the surface of the hypercrosslinked polyaniline has micropores and mesopores, the micropore size is 1.4±0.2 nm, the mesopore size is 3-10 nm, and the specific surface area is 150-650 m 2 / g; the dosage of the hypercrosslinked polyaniline in the wastewater is 60-130 mg / L.

[0009] The particle size of the hypercrosslinked polyaniline is 300-400 nm.

[0010] Preferably, the concentration of the organic dye in the organic wastewater is 50-200 mg / g; preferably 60-130 mg / L.

[0011] Preferably, the types of the organic dyes include any one or more of malachite green, rhodamine B, methyl orange, methylene blue, and congo red. Further preferably, the types of the organic dyes are rhodamine B and malachite green.

[0012] Preferably, the proportion of pores with a pore diameter of 2-10 nm in the adsorbent is greater than 50%, and the specific surface area of the adsorbent is 177-625 m 2 / g; more preferably 530-625 m 2 / g.

[0013] More preferably, the proportion of pores with a pore diameter of 2-10 nm in the adsorbent is greater than 60%, and most preferably 70%. Pores smaller than 10 nm can provide an entry channel for small molecules in the water body, facilitating the full wetting of the adsorbent by the water body. In the pores within this range, a large pore volume and specific surface area can be maintained, and a large number of pollutants can be adsorbed.

[0014] Preferably, the adsorption temperature is 20-30 °C, and the adsorption time is 4-24 h, preferably 20-24 h.

[0015] Preferably, the hypercrosslinked polyaniline is prepared by Friedel-Crafts alkylation reaction using polystyrene@polyaniline composite microspheres as building units and octavinylsilsesquioxane as a crosslinking agent.

[0016] The adsorbent is preferably prepared by Friedel-Crafts alkylation reaction of octavinylsilsesquioxane and polystyrene@polyaniline with a mass ratio of 0.8 - 1.0:1; the octavinylsilsesquioxane and polystyrene@polyaniline with this mass ratio can ensure that the adsorbent has a high crosslinking density, making the adsorbent microscopically crosslinked network-like, facilitating the adsorbent to enter the network structure for adsorption, while ensuring the number of micropores and mesopores inside the adsorbent, making the number of pores inside the adsorbent uniform and showing a certain distribution pattern, which is beneficial to the entry and movement of dye molecules and also beneficial to capturing dye molecules, doubling the adsorption rate and adsorption capacity for dye molecules.

[0017] Preferably, the Friedel-Crafts alkylation reaction includes the following steps:

[0018] (1) Under argon protection, quickly put the catalyst, octavinyl POSS and dichloroethane (DCE) into the reaction system and stir.

[0019] (2) Then add the polystyrene@polyaniline composite microspheres (PS@PANI) into the above reaction system, heat the mixture for reaction, and add methanol or deionized water to terminate the reaction.

[0020] (3) Filter and recover the black powder, wash it until the pH of the filtrate is neutral (pH = 7.0 ± 0.2) to obtain the crude product.

[0021] (4) Purify the crude product to remove unreacted octavinyl POSS, PS@PANI composite microspheres and the catalyst; then perform vacuum drying treatment to obtain hypercrosslinked polyaniline (abbreviation: PS-HCPs).

[0022] Preferably, the catalyst in step (1) is anhydrous aluminum trichloride, and the mass-volume ratio (ml / g) of anhydrous aluminum trichloride to octavinyl POSS is 1:35 - 45.

[0023] Preferably, the stirring time in step (1) is 0.5 - 1.5 h.

[0024] Preferably, the mass ratio of polystyrene@polyaniline composite microspheres to octavinylsilsesquioxane (octavinyl POSS) in step (2) is 1:0.1 - 1.5, preferably 1:0.6 - 1.2, more preferably 1:0.8 - 1.0; even more preferably 1:0.95 - 1.05.

[0025] Preferably, the reaction temperature in step (2) is 60 - 120 °C, more preferably 80 - 85 °C, and the reaction time is 12 - 36 h, more preferably 22 - 26 h.

[0026] Preferably, in step (2), the mass ratio of polystyrene@polyaniline composite microspheres to anhydrous aluminum trichloride is 1:1.5 - 2.5, and more preferably 1:1.95 - 2.05.

[0027] Preferably, in step (2), the mass ratio of polystyrene to polyaniline in the polystyrene@polyaniline composite microspheres is 0.16 - 0.20:1. The particle size of the polystyrene@polyaniline composite microspheres is 280 - 320 nm.

[0028] More preferably, in step (2), the polystyrene@polyaniline composite microspheres are prepared by polymerization with aniline using acrylic acid-functionalized polystyrene microspheres as a template. Among them, the particle size of the acrylic acid-functionalized polystyrene microspheres is 260 nm.

[0029] More preferably, in step (2), the content of acrylic acid in the polystyrene@polyaniline composite microspheres is 1.6 - 1.8%.

[0030] The functions of acrylic acid include two aspects. During the synthesis of polystyrene spheres, a small amount of acrylic acid can act as a nucleating agent. Secondly, during the preparation of PS@PANI, the acid groups derived from poly(styrene - acrylic acid) spheres can also adsorb aniline through acid-base interactions, enabling aniline to be well assembled on the surface of poly(styrene - acrylic acid) spheres.

[0031] Preferably, in step (4), the crude product is purified by Soxhlet extraction using dichloroethane, DMF, and methanol as solvents respectively.

[0032] Preferably, in step (4), the vacuum drying time is 18 - 30 h, and the vacuum drying temperature is 55 - 65 °C.

[0033] Advantages of the present invention:

[0034] Compared with the prior art, one or more technical solutions provided by the specific embodiments of the present invention have at least the following advantages:

[0035] (1) The hypercrosslinked polyaniline of the present invention has a large specific surface area. When dye molecules enter the adsorbent, it can provide sufficient adsorption sites for the adsorption of dye molecules, and malachite green (MG) and rhodamine B (RhB) in water can enter the interior of the adsorbent from the micropores and mesopores of the adsorbent and be adsorbed, improving the adsorption capacity for malachite green and rhodamine B, and solving the problems of small specific surface area and low adsorption capacity of the existing adsorbents for malachite green and rhodamine B in water. The present invention uses hypercrosslinked polyaniline to treat malachite green and rhodamine B in organic wastewater. Under the following adsorption conditions: adsorbent dosage 100 mg / L, adsorption time 24 h, temperature 25 °C, initial concentration 200 mg / L, the equilibrium adsorption capacity (Qe ) can reach 732 mg / g and -1 1108 mg / g respectively. -1 .

[0036] (2) For the adsorbent of the present invention, octavinylsilsesquioxane with more functional groups and higher reactivity is selected as the crosslinking agent to prepare a hybrid hypercrosslinked polyaniline with a high specific surface area, so as to improve the adsorption rate and adsorption capacity of organic dyes in water. The adsorbent has a high crosslinking density, making the adsorbent microscopically crosslinked network-like, facilitating the entry of dye molecules into the crosslinked network structure for adsorption, while ensuring the number of micropores and mesopores inside the adsorbent, which is beneficial to the infiltration of dye molecules and can effectively capture dye molecules, thereby doubling the adsorption rate and adsorption capacity for dye molecules. Brief Description of the Drawings

[0037] Figure 1 XRD patterns of PS-HCPs obtained from different examples.

[0038] Figure 2 SEM images of PS-HCPs obtained from different examples.

[0039] Figure 3 FI-IR spectra of PS-HCPs obtained from different examples.

[0040] Figure 4 N2 adsorption isotherms (a) and pore size distribution curves (b) of PS-HCPs obtained from different examples.

[0041] Figure 5 TGA curves of PS-HCPs obtained from different examples.

[0042] Figure 6 Effect of adsorption time on the adsorption of organic dyes by PS-HCP-3.

[0043] Figure 7 Effect of initial concentration on the adsorption of organic dyes by PS-HCP-3.

[0044] Figure 8 Recycling performance of hypercrosslinked polyaniline PS-HCPs. Detailed Embodiments

[0045] To further understand the present invention, the preferred embodiments of the present invention will be further described below in conjunction with specific examples and drawings. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein.

[0046] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular forms are also intended to include the plural forms. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they specify the presence of features, steps, operations, and / or combinations thereof.

[0047] The polystyrene@polyaniline composite microspheres (PS@PANI composite microspheres) used in the present invention can be prepared by the following method:

[0048] (1) Preparation of functionalized polystyrene microspheres:

[0049] Under a N2 atmosphere, acrylic acid and styrene (volume ratio 1:9) were added to an aqueous solution containing an initiator at a mass percentage of 0.08 - 0.11% to obtain a mixed reaction solution; it was rapidly stirred for 15 - 25 min and polymerized at 78 - 82 °C. When the color of the mixture system showed light blue, the stirring rate was reduced and the reaction was maintained until the styrene odor disappeared. Subsequently, the temperature was raised to 84 - 86 °C and the reaction was carried out for 25 - 35 min, and then cooled to room temperature to obtain the functionalized polystyrene emulsion. The initiator was ammonium persulfate or potassium persulfate.

[0050] (2) Preparation of polystyrene@polyaniline composite microspheres:

[0051] At 0 - 5 °C, the functionalized polystyrene emulsion, deionized water, and aniline were mixed and stirred for 45 - 75 min to uniformly disperse the functionalized polystyrene and aniline in the solution; dilute hydrochloric acid was added until the molar concentration of HCl in the system was 0.06 - 0.07 mol / L; then an ammonium persulfate solution was dropped into the reaction system and the reaction was carried out for 10 - 15 h. The product was washed with deionized water multiple times and then filtered under reduced pressure, and the dried product was the PS@PANI composite microspheres.

[0052] The volume ratio of the functionalized polystyrene emulsion to aniline was 7.5 - 8.5:1; the addition amount of ammonium persulfate in the reaction system was 0.02 - 0.03 mol / L.

[0053] Specifically, the specific preparation method of the polystyrene@polyaniline composite microspheres (PS@PANI composite microspheres) used in the examples and comparative examples of the present invention is as follows:

[0054] (1) Preparation of functionalized polystyrene microspheres:

[0055] Add 0.1 g of K2S2O8 and 95 mL of deionized water to a 250 mL single-necked flask, and stir to dissolve K2S2O8. Then add 0.5 mL of acrylic acid and 4.5 mL of styrene to this solution under a N2 atmosphere, and stir rapidly for 20 min to fully emulsify the added monomers. Then carry out polymerization at 80 °C. When the color of the mixture system shows slightly blue, reduce the stirring rate and keep reacting until the smell of styrene disappears. Subsequently, raise the temperature to 85 °C, react for 0.5 h, and cool down to room temperature to obtain the functionalized polystyrene emulsion.

[0056] (2) Preparation of polystyrene@polyaniline composite microspheres:

[0057] At 0 - 5 °C, add 20 mL of the prepared functionalized polystyrene emulsion, 977.5 mL of deionized water, and 2.5 mL of aniline to a 2000 mL beaker, and stir magnetically for 1 h to uniformly disperse polystyrene and aniline in the solution. Add 500 mL of HCl solution (0.2 M) under stirring. Subsequently, drop 100 mL of a solution containing 6.2 g of ammonium persulfate into the reaction system, and terminate the reaction after 12 h. The product is washed with deionized water multiple times and then filtered under reduced pressure. After drying, the product is the PS@PANI composite microspheres.

[0058] The octavinylsilsesquioxane of the present invention can be prepared by those skilled in the art through conventional methods. In a preferred embodiment of the present invention, a preparation method of octavinylsilsesquioxane (OVS) is provided. Octavinylsilsesquioxane is prepared by hydrolyzing vinyltrimethoxysilane in a mixed solution of acetone, hydrochloric acid, and water. Among them, the hydrochloric acid is concentrated hydrochloric acid (mass fraction is 36%). The specific preparation method is as follows: Add 30 mL of vinyltrimethoxysilane to 150 mL of acetone, then successively add 80 mL of concentrated hydrochloric acid and 80 mL of water, react at room temperature for 48 - 72 h (preferably 72 h), filter by suction, and wash the filter cake with acetone and absolute ethanol multiple times to obtain octavinylsilsesquioxane (OVS).

[0059] Example 1

[0060] Prepare hypercrosslinked polyaniline using polystyrene@polyaniline composite microspheres as building units, including the following steps:

[0061] Under argon protection, 1.00 g of polystyrene@polyaniline composite microspheres were added to a 50 mL round-bottom flask. 0.60 g, 0.8 g, and 1.0 g of octavinylsilsesquioxane, 2.00 g of anhydrous AlCl3, and 40 mL of 1,2-dichloroethane were taken respectively, and magnetically stirred for 1 h. The temperature was raised to 80 °C and the reaction was maintained at this temperature for 24 h. Then, filtration was carried out, and the product was washed successively with distilled water and absolute ethanol. Then the product was placed in a Soxhlet extractor and purified with methanol, dichloroethane, and N,N-dimethylformamide as solvents for 48 h each, and vacuum dried at 60 °C for 24 h to obtain hypercrosslinked polyaniline (denoted as PS-HCP-1, PS-HCP-2, PS-HCP-3).

[0062] Comparative Example 1

[0063] A preparation method of hypercrosslinked polyaniline. Under Ar protection, 0.5 g of hollow spherical polyaniline (HSPANI) and 0.4 g of octavinyl POSS were added to a 100 mL single-necked flask containing 40 mL of dichloroethane. After the mixture was stirred for 0.5 h, 1.0 g of anhydrous aluminum trichloride was added. The reaction was terminated after reacting at 80 °C for 24 h. Filtration was carried out under reduced pressure to collect the product. The product was Soxhlet extracted with methanol, dichloroethane, and DMF as solvents for 48 h respectively to remove the catalyst, unreacted POSS, and HSPANI. The purified product was wrapped with filter paper and first dried with a hair dryer. After the solvent volatilized to a trace amount, it was then dried in a vacuum drying oven at 60 °C for 24 h to finally obtain HCPP-3.

[0064] Product performance test:

[0065] (1) Figure 1 XRD patterns of PS@PANI composite microspheres, PS-HCP-1, PS-HCP-2, and PS-HCP-3 are shown. PS@PANI has two sharp diffraction peaks at 2θ = 20.20° and 24.58°, indicating that PS@PANI is in a semi-crystalline state. After the reaction of PS@PANI with octavinyl POSS, the peak at 2θ = 24.58° on the XRD of PS-HCP-1 to PS-HCP-3 disappears, and only a broad diffraction peak exists at about 2θ = 21°, showing the amorphous nature of PS-HCPs; the results indicate that PS@PANI reacts with octavinyl POSS.

[0066] (2) Figure 2 SEM images of PS@PANI, PS-HCP-1, PS-HCP-2, and PS-HCP-3 are shown. It can be seen that the surface of the PS@PANI composite microspheres ( Figure 2 , a) is rough, with a regular shape and structure, and relatively uniform size. The particle size is about 300 nm, and only a very small part agglomerates together. Figure 3, b, c, and d are SEM images of PS-HCP-1, PS-HCP-2, and PS-HCP-3, respectively. It can be found that PS-HCPs have a rough surface morphology and are composed of many spherical particles stacked into a block structure to form a porous structure. In addition, the hollow structure of some particles may be caused by the removal of unreacted polystyrene balls after Soxhlet extraction. Combined with XRD analysis, PS-HCPs are amorphous non-crystalline polymers.

[0067] (3) Figure 3 Fourier transform infrared spectra (FI-IR) of PS@PANI, PS-HCP-1, PS-HCP-2, and PS-HCP-3. PS@PANI has the following peaks at 3400, 2912, 1565, 1486, 1301, 1274, 1144, 802, and 697 cm -1 The characteristic peaks at 1096cm correspond to the stretching vibration of NH, the stretching vibration of CH on polystyrene CH2, the stretching vibration of C=N quinone ring, the stretching vibration of C=C on benzene ring, the stretching vibration of CN, the stretching vibration of CO on carboxyl functionalized polystyrene, the stretching vibration of quinone structure N=Q=N, the bending vibration out of the plane of CH bond and the bending vibration of CH of monosubstituted benzene (five adjacent hydrogens) on benzene ring of carboxyl functionalized polystyrene. For PS-HCPs, after the reaction of PS@PANI with octaethylene POSS, PS-HCPs have a peak at 1096cm -1 The characteristic peak of Si-O-Si bond appears at about 2929 cm -1 The peak intensities at 1715 and 1274 cm-1 increased to varying degrees, indicating that the CH2 content increased, indicating that the PS@PANI microspheres and octaethylene POSS successfully underwent Friedel-Crafts reaction, and the reaction extents were different. -1 The characteristic peak at 697 cm is the stretching vibration peak of C=O and CO on the carboxyl functionalized polystyrene in the PS@PANI composite microspheres, and the original PS@PANI -1 The characteristic absorption peak of monosubstituted benzene disappeared after reacting with POSS, indicating that the benzene ring on PS@PANI polystyrene also participated in the Frediel-Crafts alkylation reaction.

[0068] (4) Figure 4Results of N2 adsorption - desorption tests (77K, 1.0 bar) for PS - HCPs. As can be seen from Figure a, the isotherm of PS - HCPs conforms to the characteristics of type IV isotherms. At low relative pressures (P / P0 < 0.001), the adsorption amount shows a vertical upward trend. At higher relative pressures (P / P0 = 0.001 - 1.0), the adsorption amount increases slowly and there is a hysteresis loop. Combining with the pore size distribution curve of PS - HCPs ( Figure 4 , b), it can be seen that PS - HCPs have micropores and mesopores. The micropores of PS - HCPs are concentrated at 1.4 nm, and the mesopores are concentrated at 3 - 10 nm. The pore parameters of PS - HCPs are shown in Table 1. From Table 1, it can be seen that the S BET values of PS - HCP - 1, PS - HCP - 2, and PS - HCP - 3 are 177, 530, and 625 m 2 g -1 respectively. In addition, PS - HCP - 2 and PS - HCP - 3 conform to H2 in type IV isotherms, indicating that there may be interstitial pores generated by the close packing of spherical particles, which is consistent with the SEM results. PS - HCP - 1 is more in line with type H3, probably due to too low cross - linking density and irregular pore structure. The S BET value of Comparative Example 1 is 342 m 2 g -1 , which may be because part of the polystyrene also participated in the reaction, resulting in a higher specific surface area.

[0069] Table 1 Pore data of HCPPs

[0070]

[0071] (5) Under N2 atmosphere, TGA tests were carried out at a heating rate of 10℃ min -1 , and the temperature range was 45 - 800℃. The results are as Figure 5As shown. For PS@PANI, the weight loss is significantly divided into four stages. In the range of 45 - 100 °C, this loss is mainly attributed to the evaporation of water. In the range of 240 °C and 350 °C, this loss may be due to the formation of polyacrylic anhydride and the decomposition of the side groups of the composite microspheres. In the range of 350 °C and 450 °C, this loss is mainly the degradation of the functionalized polystyrene molecular chain and polyaniline. In the range of 450 °C and 580 °C, this loss is the further degradation of the polyaniline molecular chain. For PS-HCPs, the mass loss in the range of 120 - 300 °C may be related to the detachment of the protonic acid doped on the main chain of polyaniline and the breakage of the unreacted vinyl groups on POSS. The mass loss in the range of 300 - 800 °C may be caused by the breakage of the Si-O-Si bonds on the POSS cage structure and the degradation of the polyaniline molecular chain. Compared with PS@PANI, PS-HCPs have less mass loss. The reason may be that the hypercrosslinked structure of PS-HCPs after the reaction of PS@PANI with POSS makes its structure not easily damaged by high temperature. In addition, the char yield of PS-HCPs is still higher than 61% at 800 °C, indicating excellent thermal stability of PS-HCPs.

[0072] Example 2

[0073] A method for treating organic dye wastewater using hypercrosslinked polyaniline PS-HCPs. Add 10 mg of PS-HCPs (PS-HCP-1, PS-HCP-2, PS-HCP-3) to 100 mL of malachite green (MG) and rhodamine B (RhB) solutions with an initial concentration of 200 mg / g, and shake with a constant temperature oscillator at a speed of 200 rpm min -1 for 24 h. The adsorption temperature is 25 °C.

[0074] The equilibrium adsorption capacity (Q e ) of PS-HCP-1 for RhB and MG is 452 and 520 mg g -1 ; the Q e of PS-HCP-2 for MG and RhB is 556 and 932 mg g -1 ; the Q e of PS-HCP-3 for MG and RhB is 732 and 1108 mg g -1 . It can be found that after reacting with PS@PANI using octavinyl POSS as the crosslinking agent, its adsorption capacity for dyes is significantly improved. The equilibrium adsorption capacity (Q e ) is the mass of the organic dye absorbed per gram of adsorbent: Q e = (C0 - C e )v / m,

[0075] where C0 and C eThey represent the initial concentration of the dye and the equilibrium concentration of the solution after the adsorption of PS-HCPs is completed (mg / L), v represents the volume of the solution (mL), and m is the mass of PS-HCPs (g). -1 )

[0076] The Q of hypercrosslinked polyaniline in Comparative Example 1 for MG and RhB e is 493.6 and 807.7 mg / g -1 . This may be because polystyrene also participates in the reaction, resulting in a higher specific surface area and improved adsorption performance.

[0077] Example 3

[0078] A method for treating organic dye wastewater using hypercrosslinked polyaniline PS-HCPs. Using PS-HCP-3 as the adsorbent and RhB as the organic dye, 5 mg of PS-HCP-3 was added to 50 mL of a solution with an initial concentration of 200 mg / L -1 . At 25 °C, adsorption was carried out for 24 h, and the change in the adsorption capacity was recorded every half hour, as Figure 6 shown. The optimal adsorption time is 4 - 24 h, preferably 20 - 24 h.

[0079] Example 4

[0080] A method for treating organic dye wastewater using hypercrosslinked polyaniline PS-HCPs. Using PS-HCP-3 as the adsorbent and RhB as the organic dye, 10 mg of PS-HCP-3 was added to 100 mL of a solution with different initial concentrations. At 25 °C, adsorption was carried out for 24 h, and the change in the removal rate of RhB was recorded, as Figure 7 shown. The suitable initial concentration range of the organic dye is 50 - 200 mg / L, preferably 60 - 130 mg / L, and the removal rate can reach over 80%.

[0081] When C0 is higher, the Q of PS-HCP-3 e is higher, but the removal rate decreases instead. This is because the number of adsorption sites of PS-HCP-3 is certain. The higher the RhB concentration, the greater the contact probability with PS-HCP-3, and the higher the utilization efficiency of the active sites, so Q e is higher. However, when the dosage of PS-HCP-3 is limited, when RhB reaches a certain concentration, the active sites will reach saturation, and too many RhB molecules will not be adsorbed on PS-HCP-3, resulting in a decrease in the removal rate as the RhB concentration increases. In addition, the molecular size of RhB is The micropores of PS-HCP-3 are distributed at 1.4 nm, and the mesopores are distributed at 3-10 nm. The abundant micropores / mesopores provide channels for capturing RhB molecules, and there is a special π-π conjugation effect and electrostatic interaction between PS-HCP-3 and RhB, resulting in a high adsorption capacity of PS-HCP-3.

[0082] The optimal adsorption conditions for rhodamine B are as follows: the adsorbent dosage is 100 mg / L, the adsorption time is 24 h, the temperature is 25 °C, and the initial concentration is 60-130 mg / L.

[0083] Example 5

[0084] Recyclability of PS-HCP-3: Add PS-HCP-3 (50 mg) to 500 mL of RhB solution with C0 of 200 mg / L. After adsorption for 24 h, measure the adsorption capacity, and use ethanol as the solvent to desorb and regenerate PS-HCP-3. As shown -1 in the figure, after three consecutive cycles, the adsorption capacity of PS-HCP-3 for RhB only decreases from 1108 mg / g Figure 8 to 922.9 mg / g -1 . After three cycles, the retention rate of the adsorption capacity of PS-HCP-3 for RhB is still higher than 83.29% (calculated based on the initial saturated adsorption capacity), indicating that PS-HCP-3 has good regeneration ability and great value in the application of sewage treatment and ecological environment restoration. -1 .

[0085] The above embodiments have described the technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, supplements, equivalent replacements, etc. made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for treating organic dye wastewater, characterized in that, Using hyper-crosslinked polyaniline as an adsorbent to adsorb organic dyes in wastewater, the specific surface area of the adsorbent is 530 - 625 m 2 / g; The hyper-crosslinked polyaniline is prepared by Friedel-Crafts alkylation reaction using polystyrene@polyaniline composite microspheres as building units and octavinylsilsesquioxane as a crosslinking agent. The mass ratio of polystyrene@polyaniline composite microspheres to octavinylsilsesquioxane is 1:0.95 - 1.05; The polystyrene@polyaniline composite microspheres are prepared by polymerizing aniline with acrylic acid-functionalized polystyrene microspheres as a template. Among them, the content of acrylic acid in the polystyrene@polyaniline composite microspheres is 1.6 - 1.8%, and the particle size of the acrylic acid-functionalized polystyrene microspheres is 260 nm.

2. The treatment method of the organic dye wastewater according to claim 1, characterized in that, The surface of the hyper-crosslinked polyaniline has micropores and mesopores. The size of the micropores is 1.4 ± 0.2 nm, and the size of the mesopores is 3 - 10 nm.

3. The treatment method of organic dye wastewater according to claim 2, wherein The particle size of the hyper-crosslinked polyaniline is 300 - 400 nm, and the proportion of pores with a pore diameter of 2 - 10 nm in the adsorbent is greater than 60%.

4. The treatment method of organic dye wastewater according to claim 3, wherein, The proportion of pores with a pore diameter of 2 - 10 nm in the adsorbent is 70%.

5. The treatment method of organic dye wastewater according to claim 1, wherein The proportion of pores with a pore diameter of 2 - 10 nm in the adsorbent is greater than 50%.

6. The treatment method of organic dye wastewater according to claim 1, wherein The dosage of the hyper-crosslinked polyaniline in the wastewater is 60 - 130 mg / L.

7. The treatment method of organic dye wastewater according to claim 1, characterized in that The concentration of the organic dye in the organic dye wastewater is 50 - 200 mg / g.

8. The treatment method of the organic dye wastewater according to claim 7, wherein, The concentration of the organic dye in the organic dye wastewater is 60 - 130 mg / L.

9. The treatment method of organic dye wastewater according to claim 1, wherein The types of the organic dye include any one or more of malachite green, rhodamine B, methyl orange, methylene blue, and congo red.

10. The treatment method of organic dye wastewater according to claim 1, characterized in that, The adsorption temperature is 20 - 30 °C, and the adsorption time is 4 - 24 h.

11. The treatment method of the organic dye wastewater according to claim 10, characterized in that, The adsorption time is 20 - 24 h.

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