Anthraquinone modified pyrite and mbb r packing composition and method of making

Abstract

The application belongs to the technical field of MBBR fillers, and particularly relates to a pyrite modified by anthraquinone and a MBBR filler composition and a preparation method thereof. The preparation method of the pyrite modified by anthraquinone comprises the following steps: performing a polymerization reaction on a carbon-carbon double bond modified pyrite, an anthraquinone-containing polymerizable monomer and other polymerizable monomers to obtain the pyrite modified by anthraquinone; and the carbon-carbon double bond modified pyrite is obtained by performing surface modification on the pyrite by using an alkenyl silane coupling agent. The anthraquinone-containing polymerizable monomer with a specific structure is prepared, and the pyrite modified by anthraquinone obtained by performing a polymerization reaction on the carbon-carbon double bond modified pyrite and the anthraquinone-containing polymerizable monomer has an antioxidant property, and can achieve a high-efficiency denitrification and dephosphorization effect and has good long-term stability in the application of the MBBR filler composition.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of MBBR fillers, and particularly relates to an anthraquinone modified pyrite and MBBR filler composition and a preparation method thereof. BACKGROUND

[0002] With the continuous development of society and industry, a large amount of nitrogen and phosphorus elements are generated in the process of human life and production and enter natural water bodies, resulting in increasingly serious water eutrophication problems, causing serious environmental problems and endangering human health. At present, nitrogen and phosphorus removal is mainly achieved through biological nitrogen and phosphorus removal. The biological nitrogen and phosphorus removal process is widely used due to its mild reaction conditions, wide application range, low cost investment, stable operation and remarkable effect. Among them, the moving bed biofilm reactor (MBBR) becomes a new type of efficient composite process treatment method due to its advantages of both traditional activated sludge process and biological contact oxidation process. However, since the microorganism needs sufficient carbon source to achieve good denitrification effect, the MBBR process needs to add additional carbon source to ensure the denitrification effect, which not only increases the operation cost but also easily causes secondary pollution due to excessive carbon source.

[0003] In recent years, the sulfur autotrophic denitrification technology has attracted widespread attention and research due to its low sludge production and no need for additional carbon source. It uses specific autotrophic denitrification microorganisms such as denitrifying sulfur bacteria to reduce nitrate nitrogen (NO 3 ) to nitrogen under anaerobic or anoxic conditions with reduced sulfur as the electron donor, thereby achieving denitrification. In addition, natural sulfur-iron compounds can provide sulfur and iron (Fe 2+ ) as electron donors, and achieve chemical phosphorus removal through the interaction between iron and phosphorus. It is considered to be an ideal choice for autotrophic denitrification electron donors, but there are problems such as low activity of natural pyrite, low efficiency of denitrification and phosphorus removal, and poor stability in the denitrification process.

[0004] In summary, how to prepare a sulfur-iron ore with antioxidant properties so that the MBBR filler composition obtained can achieve efficient denitrification and phosphorus removal effect and has long-term stability in the wastewater treatment process is a technical problem that needs to be solved at present. SUMMARY

[0005] The present application provides a preparation method of anthraquinone modified pyrite with antioxidant properties to overcome the defects of low activity, low efficiency of denitrification and phosphorus removal, and poor long-term stability of natural pyrite, and applies it to MBBR filler composition, which can achieve efficient denitrification and phosphorus removal effect and has good long-term stability in the wastewater treatment process.

[0006] Specifically, the preparation method of the anthraquinone modified pyrite comprises: performing a polymerization reaction on a carbon-carbon double bond modified pyrite, an anthraquinone-containing polymerizable monomer and other polymerizable monomers, to obtain the anthraquinone modified pyrite; the carbon-carbon double bond modified pyrite is obtained by performing surface modification on the pyrite by using an alkenyl silane coupling agent; the anthraquinone-containing polymerizable monomer has a structure shown in formula (1).

[0007]

[0008] In formula (1), R1 is -O- or -NH-, R2 is H, a hydroxyl group, an amino group, an amino derivative or a C1-C5 alkyl group.

[0009] Preferably, the mass ratio of the carbon-carbon double bond modified pyrite, the anthraquinone-containing polymerizable monomer and the other polymerizable monomers is 1:(0.03-0.5):(0.05-0.2).

[0010] Preferably, the average particle size of the pyrite is 1-100 μm.

[0011] Preferably, the other polymerizable monomer has a structure shown in formula (2).

[0012]

[0013] In formula (2), R3 is -NH2 or -OR4, and R4 is H or a C1-C5 alkyl group.

[0014] Preferably, the other polymerizable monomer is at least one selected from hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylamide, methyl acrylate and ethyl acrylate.

[0015] Preferably, the polymerization reaction is performed in water or an organic solvent.

[0016] Preferably, when the solvent is water, a surfactant is further added.

[0017] Preferably, the preparation method of the anthraquinone-containing polymerizable monomer comprises performing surface modification on (amino-hydroxyl) anthraquinone by using acrylic acid, to obtain the anthraquinone-containing polymerizable monomer having the structure shown in formula (1).

[0018] The application provides the anthraquinone modified pyrite prepared by the above method.

[0019] The application further provides an MBBR filler composition.

[0020] The MBBR filler composition provided by the application comprises polyolefin, the anthraquinone modified pyrite prepared by the above method, maleic anhydride grafted polyolefin, an antioxidant, an ultraviolet resistant agent and inorganic filler.

[0021] Preferably, the mass ratio of the polyolefin, the anthraquinone-modified pyrite, the maleic anhydride grafted polyolefin, the antioxidant, the ultraviolet resistant agent, and the inorganic filler is 100:(1-20):(1-10):(0.5-1.5):(0.3-2):(5-50).

[0022] The key of the application is to prepare an anthraquinone-modified pyrite by preparing an anthraquinone-containing polymerizable monomer with a specific structure, and performing a polymerization reaction with a carbon-carbon double bond modified pyrite, thereby improving the biochemical reaction rate of sulfur autotrophic denitrification, and at the same time, the anthraquinone-modified pyrite obtained by polymerizing the carbon-carbon double bond modified pyrite with the anthraquinone-containing polymerizable monomer and other polymerizable monomers is stable in structure and is not easy to be oxidized in the process of denitrification and phosphorus removal, thereby ensuring that it has good long-term stability. In addition, the anthraquinone-modified pyrite is applied to the MBBR filler composition, and in the process of wastewater treatment, high-efficiency denitrification and phosphorus removal effect can be achieved. DETAILED DESCRIPTION

[0023] The preparation method of the anthraquinone-modified pyrite provided by the application comprises performing a polymerization reaction on a carbon-carbon double bond modified pyrite, an anthraquinone-containing polymerizable monomer, and other polymerizable monomers, and obtaining the anthraquinone-modified pyrite.

[0024] In a preferred embodiment, the conditions of the polymerization reaction include a temperature of 80-120°C, such as 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any value therebetween; and a time of 4-8h, such as 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, or any value therebetween.

[0025] In a preferred embodiment, the polymerization reaction is performed in the following manner: the carbon-carbon double bond modified pyrite is uniformly dispersed in a solvent, the anthraquinone-containing polymerizable monomer and other polymerizable monomers are added under nitrogen protection, and the temperature is raised to 80-120°C, and the reaction is continued for 4-8h. After the temperature is lowered to room temperature, the solvent is removed and washed and dried, and the anthraquinone-modified pyrite is obtained.

[0026] In a preferred embodiment, the solvent used in the above polymerization reaction is water or an organic solvent, and specific examples of the organic solvent include, but are not limited to, at least one of methanol, ethanol, acetone, triethanolamine, and N,N-dimethylformamide.

[0027] In a preferred embodiment, when the solvent used in the polymerization reaction described above is water, a surfactant is also added. Preferably, the surfactant is selected from at least one of sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, sorbitan fatty acid ester, pentaerythritol stearate, sodium perfluorononenyloxybenzenesulfonate, distearyldimonium chloride lauryl glutamate, and cocamidopropyl betaine. Preferably, the amount of surfactant added is 0.3-2% by weight of the solvent, such as 0.3%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, or any value therebetween.

[0028] In a preferred embodiment, the mass ratio of the carbon-carbon double bond modified pyrite to anthraquinone-containing polymerizable monomer is 1 : (0.03-0.5), such as 1 :0.03, 1 :0.05, 1 :0.08, 1 :0.1, 1 :0.15, 1 :0.2, 1 :0.25, 1 :0.3, 1 :0.35, 1 :0.4, 1 :0.45, 1 :0.5, or any value therebetween. The mass ratio of the carbon-carbon double bond modified pyrite to other polymerizable monomer is 1 : (0.05-0.2), such as 1 :0.05, 1 :0.08, 1 :0.1, 1 :0.12, 1 :0.15, 1 :0.18, 1 :0.12, or any value therebetween.

[0029] In a preferred embodiment, the carbon-carbon double bond modified pyrite is obtained by surface modification of pyrite with an alkenyl silane coupling agent. In a specific embodiment, the surface modification method is to add pyrite into a mixed solvent of ethanol and water, add the alkenyl silane coupling agent under the protection of nitrogen, and then react in an oil bath at a temperature of 70-90 °C for 10-16 h. After the product is washed with anhydrous ethanol and dried under vacuum at 75-85 °C, the carbon-carbon double bond modified pyrite is obtained.

[0030] In a preferred embodiment, the mass ratio of the pyrite to the alkenyl silane coupling agent is 1 : (0.2-0.4), such as 1 :0.2, 1 :0.25, 1 :0.3, 1 :0.35, 1 :0.4, or any value therebetween.

[0031] In a preferred embodiment, specific examples of the alkenyl silane coupling agent include, but are not limited to, at least one of (meth)acryloxypropyl silane coupling agent, vinyltrichlorosilane, vinyltrimethoxysilane, dichloromethylvinylsilane, and chloro(dimethyl)vinylsilane.

[0032] In a preferred embodiment, the average particle size of the pyrite is 1-100 μm, such as 1 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any value therebetween.

[0033] In a preferred embodiment, the other polymerizable monomer can have a structure represented by Formula (2). In Formula (2), R3 is -NH2 or -OR4, and R4 is H or a C1-C5 alkyl group. Specific examples of the C1-C6 alkyl group include, but are not limited to, at least one of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, and neopentyl. From the perspective of easy availability of raw materials, the other polymerizable monomer can be at least one of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, methyl acrylate, and ethyl acrylate.

[0034]

[0035] In a preferred embodiment, the method for preparing the anthraquinone-containing polymerizable monomer includes surface modification of (amino-hydroxy)anthraquinone with acrylic acid to obtain an anthraquinone-containing polymerizable monomer having a structure represented by Formula (1). In a specific embodiment, the surface modification method includes mixing (amino-hydroxy)anthraquinone with a dichloromethane solution, adding a catalyst and a dehydrating agent, heating to 40-80°C under a nitrogen atmosphere, dropwise adding acrylic acid, heating to reflux at 100-140°C for 8-16 h, washing the product, and drying the product at 80°C under vacuum to obtain the anthraquinone-containing polymerizable monomer.

[0036]

[0037] In Formula (1), R1 is -O- or -NH-, and R2 is H, a hydroxyl group, an amino group, an amino derivative, or a C1-C5 alkyl group.

[0038] In a preferred embodiment, the mass ratio of the (amino-hydroxy)anthraquinone and the catalyst is 1 : (0.05-0.2), such as 1 :0.05, 1 :0.08, 1 :0.1, 1 :0.12, 1 :0.15, 1 :0.18, 1 :0.2, or any value therebetween. The mass ratio of the (amino-hydroxy)anthraquinone and the dehydrating agent is 1 : (0.1-0.2), such as 1 :0.1, 1 :0.12, 1 :0.15, 1 :0.18, 1 :0.2, or any value therebetween. The mass ratio of the (amino-hydroxy)anthraquinone and the acrylic acid is 1 : (0.24-0.4), such as 1 :0.24, 1 :0.28, 1 :0.3, 1 :0.32, 1 :0.35, 1 :0.38, 1 :0.4, or any value therebetween.

[0039] In a preferred embodiment, the (amino-hydroxy)anthraquinone can be at least one of diaminianthraquinone, dihydroxyanthraquinone, and amino-hydroxyanthraquinone, specific examples of which include, but are not limited to, at least one of 1,2-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1 -amino-4-hydroxyanthraquinone, 2-amino-3-hydroxyanthraquinone, 1,2-diaminianthraquinone, and 1,4-diaminianthraquinone.

[0040] In a preferred embodiment, specific examples of the catalyst include, but are not limited to, at least one of triethylamine, N,N-dimethylbenzylamine, and 4-dimethylaminopyridine.

[0041] In the present application, the anthraquinone-modified pyrite described above is applied to an MBBR filler composition. The MBBR filler composition includes a polyolefin, an anthraquinone-modified pyrite, a maleic anhydride grafted polyolefin, an antioxidant, an ultraviolet light resistant agent, and an inorganic filler. The content of the anthraquinone-modified pyrite is 1-20 parts by weight, such as 1, 2, 5, 10, 12, 15, 18, 20 parts by weight, or any value therebetween, based on 100 parts by weight of the polyolefin; the content of the maleic anhydride grafted polyolefin is 1-10 parts by weight, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight, or any value therebetween; the content of the antioxidant is 0.5-1.5 parts by weight, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 parts by weight, or any value therebetween; the content of the ultraviolet light resistant agent is 0.3-2 parts by weight, such as 0.3, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0 parts by weight, or any value therebetween; and the content of the inorganic filler is 5-50 parts by weight, such as 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50 parts by weight, or any value therebetween.

[0042] In a preferred embodiment, the polyolefin is at least one of a homopolymer and / or a copolymer. Preferably, specific examples of the polyolefin include, but are not limited to, at least one of polyethylene, polypropylene, polybutene, polyamylene, polyhexene, and polyoctene.

[0043] In a preferred embodiment, the antioxidant is at least one of tea polyphenol, butylated hydroxyl anisole, butylated hydroxyl toluene, tertiary butyl hydroquinone, antioxidant 1010, and antioxidant 1076.

[0044] In a preferred embodiment, the anti-UV agent is at least one of salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine. Preferably, the anti-UV agent can be specifically UV absorber 1130 and / or UV absorber UV-531.

[0045] In a preferred embodiment, the inorganic filler is at least one of calcium carbonate, talc powder, quartz powder, mica powder, titanium white powder, white carbon black, bentonite, carbon black, aluminum hydroxide, and aluminum oxide.

[0046] The present application will be described in detail below through specific examples.

[0047] In the following examples and comparative examples, the parts of the raw materials refer to weight parts.

[0048] In the following examples and comparative examples:

[0049] The polypropylene is a homopolymer polypropylene, and the melt index thereof under the action of 2.16 kg at 190°C is 5 g / 10 min.

[0050] The melt index of the maleic anhydride grafted polypropylene under the action of 2.16 kg at 190°C is 8 g / 10 min, and the grafting rate of maleic anhydride is 2.8%.

[0051] Preparation of carbon-carbon double bond modified pyrite

[0052] 5 g of pyrite (average particle size of 50 μm) is uniformly dispersed in a mixed solvent of ethanol and water, 1 g of vinyltrichlorosilane is added under the protection of nitrogen, and after oil bath reaction at a temperature of 80°C for 12 h, the product is washed with anhydrous ethanol for three times, and then dried under vacuum at 80°C for 12 h to obtain the carbon-carbon double bond modified pyrite.

[0053] Preparation of carbon-carbon double bond modified pyrite

[0054] 5g of pyrite (average particle size of 50 μm) was uniformly dispersed in a mixed solvent of ethanol and water, 1.5g of dichloromethylvinylsilane was added under nitrogen protection, and after oil bath reaction at a temperature of 80°C for 12h, the product was washed with anhydrous ethanol three times and dried under vacuum at 80°C for 12h to obtain carbon-carbon double bond modified pyrite.

[0055] Preparation of carbon-carbon double bond modified pyrite

[0056] 5g of pyrite (average particle size of 50 μm) was uniformly dispersed in a mixed solvent of ethanol and water, 2g of (methyl) acryloyloxypropyl silane coupling agent was added under nitrogen protection, and after oil bath reaction at a temperature of 80°C for 12h, the product was washed with anhydrous ethanol three times and dried under vacuum at 80°C for 12h to obtain carbon-carbon double bond modified pyrite.

[0057] Example 1

[0058] (1) Preparation of anthraquinone-containing polymerizable monomer:

[0059] 12g of 1-amino-4-hydroxyanthraquinone was mixed with dichloromethane solution, 0.6g of 4-dimethylaminopyridine catalyst and 1.2g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (dehydrating agent) were added, heated to 60°C under nitrogen atmosphere, 2.9g of acrylic acid was added dropwise, heated to reflux at 120°C for 12h, the product was washed and dried under vacuum at 80°C for 12h to obtain anthraquinone-containing polymerizable monomer A1.

[0060] (2) Preparation of anthraquinone-modified pyrite:

[0061] 5g of carbon-carbon double bond modified pyrite of Preparation Example 1 was uniformly dispersed in 30mL of N,N-dimethylformamide, 0.15g of anthraquinone-containing polymerizable monomer A1 and 1g of ethyl acrylate were added under nitrogen protection, and the temperature was raised to 105°C, and the reaction was continued for 6h, after the temperature was lowered to room temperature, the solvent was removed and washed and dried to obtain anthraquinone-modified pyrite.

[0062] (3) Preparation of MBBR filler composition:

[0063] 100 parts of polypropylene, 2 parts of anthraquinone-modified pyrite, 10 parts of maleic anhydride grafted polyolefin, 1.5 parts of antioxidant (antioxidant 1010), 2 parts of ultraviolet resistant agent (ultraviolet absorber 1130) and 5 parts of inorganic filler (silicon dioxide) were weighed into a dispersion mixing device and uniformly mixed, then sent to a granulator for solidification and granulation, and the obtained granular material was dried to obtain the MBBR filler composition.

[0064] Example 2

[0065] (1) Preparation of anthraquinone-containing polymerizable monomer:

[0066] In a mixture of 12 g of 1-amino-4-hydroxyanthraquinone and dichloromethane, 1.4 g of 4-dimethylaminopyridine catalyst and 1.8 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (dehydrating agent) were added, and 3.7 g of acrylic acid was added dropwise under a nitrogen atmosphere heated to 60°C, and the reaction was heated to reflux at 120°C for 12 h. The product was washed and dried at 80°C under vacuum for 12 h to obtain anthraquinone-containing polymerizable monomer A2.

[0067] (2) Preparation of anthraquinone-modified pyrite:

[0068] 5 g of carbon-carbon double bond-modified pyrite prepared in Preparation Example 2 was uniformly dispersed in 30 mL of N,N-dimethylformamide, 1.5 g of anthraquinone-containing polymerizable monomer A2 and 0.75 g of ethyl acrylate were added under nitrogen protection, and the temperature was raised to 105°C, and the reaction was continued for 6 h. After cooling to room temperature, the solvent was removed and washed and dried to obtain anthraquinone-modified pyrite.

[0069] (3) Preparation of MBBR filler composition:

[0070] 100 parts of polypropylene, 10 parts of anthraquinone-modified pyrite, 6 parts of maleic anhydride-grafted polyolefin, 1 part of antioxidant (antioxidant 1010), 1 part of ultraviolet-resistant agent (ultraviolet absorber 1130), and 25 parts of inorganic filler (silicon dioxide) were weighed into a dispersion mixing device and mixed uniformly, and then fed into a granulator for solidification and granulation. The obtained granular material was dried to obtain the MBBR filler composition.

[0071] Example 3

[0072] (1) Preparation of anthraquinone-containing polymerizable monomer:

[0073] In a mixture of 12 g of 1-amino-4-hydroxyanthraquinone and dichloromethane, 2.4 g of 4-dimethylaminopyridine catalyst and 2.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (dehydrating agent) were added, and 4.2 g of acrylic acid was added dropwise under a nitrogen atmosphere heated to 60°C, and the reaction was heated to reflux at 120°C for 12 h. The product was washed and dried at 80°C under vacuum for 12 h to obtain anthraquinone-containing polymerizable monomer A3.

[0074] (2) Preparation of anthraquinone-modified pyrite:

[0075] Disperse 5 g of carbon-carbon double bond modified pyrite of Preparation Example 3 in 30 mL of N,N-dimethylformamide, add 2.5 g of anthraquinone-containing polymerizable monomer A3 and 0.25 g of ethyl acrylate under nitrogen protection, and heat to 105°C, continue to react for 6 h, after cooling to room temperature, remove the solvent and clean, dry, to obtain anthraquinone-modified pyrite.

[0076] (3) Preparation of MBBR filler composition:

[0077] Take 100 parts of polypropylene, 20 parts of anthraquinone-modified pyrite, 2 parts of maleic anhydride grafted polyolefin, 0.5 parts of antioxidant (antioxidant 1010), 0.3 parts of ultraviolet resistant agent (ultraviolet absorber 1130) and 50 parts of inorganic filler (silicon dioxide) into a dispersion mixing device, mix uniformly, then send into a granulator for solidification and granulation, and the obtained granular material is dried to obtain the MBBR filler composition.

[0078] Example 4

[0079] (1) Preparation of anthraquinone-containing polymerizable monomer:

[0080] Mix 12 g of 1-amino-4-hydroxyanthraquinone with a dichloromethane solution, add 1.4 g of 4-dimethylaminopyridine catalyst and 1.8 g of 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (dehydrating agent), heat to 60°C under nitrogen atmosphere, add 3.7 g of acrylic acid dropwise, heat to reflux at 120°C for 12 h, wash the product, and dry at 80°C under vacuum for 12 h to obtain the anthraquinone-containing polymerizable monomer A4.

[0081] (2) Preparation of anthraquinone-modified pyrite:

[0082] Disperse 5 g of carbon-carbon double bond modified pyrite of Preparation Example 2 in 30 mL of a solution of water and 0.3 g of sodium dodecylbenzenesulfonate, add 1.5 g of anthraquinone-containing polymerizable monomer A4 and 0.75 g of ethyl acrylate under nitrogen protection, and heat to 105°C, continue to react for 6 h, after cooling to room temperature, remove the solvent and clean, dry, to obtain anthraquinone-modified pyrite.

[0083] (3) Preparation of MBBR filler composition:

[0084] Take 100 parts of polypropylene, 10 parts of anthraquinone-modified pyrite, 6 parts of maleic anhydride grafted polyolefin, 1 part of antioxidant (antioxidant 1010), 1 part of ultraviolet resistant agent (ultraviolet absorber 1130) and 25 parts of inorganic filler (silicon dioxide) into a dispersion mixing device, mix uniformly, then send into a granulator for solidification and granulation, and the obtained granular material is dried to obtain the MBBR filler composition.

[0085] Example 5

[0086] The anthraquinone-containing polymerizable monomer, anthraquinone-modified pyrite and MBBR filler composition were prepared according to the method of Example 2, except that 1-amino-4-hydroxyanthraquinone was replaced with the same mass of 1,4-diaminoanthraquinone, and the rest of the conditions were the same.

[0087] Example 6

[0088] The anthraquinone-containing polymerizable monomer, anthraquinone-modified pyrite and MBBR filler composition were prepared according to the method of Example 2, except that 1-amino-4-hydroxyanthraquinone was replaced with the same mass of 1,4-diaminoanthraquinone, and the rest of the conditions were the same.

[0089] Comparative Example 1

[0090] (1) Preparation of reference pyrite:

[0091] 5 g of carbon-carbon double bond modified pyrite prepared in Preparation Example 2 was uniformly dispersed in 30 mL of N,N-dimethylformamide, 0.75 g of ethyl acrylate was added under nitrogen protection, and the temperature was raised to 105°C, and the reaction was continued for 6 h. After cooling to room temperature, the solvent was removed and washed and dried to obtain the reference modified pyrite.

[0092] (2) Preparation of reference MBBR filler composition:

[0093] 100 parts of polypropylene, 10 parts of reference modified pyrite, 6 parts of maleic anhydride grafted polyolefin, 1 part of antioxidant (antioxidant 1010), 1 part of ultraviolet resistant agent (ultraviolet absorber 1130) and 25 parts of inorganic filler (silicon dioxide) were weighed into a dispersion mixing device and mixed uniformly, then sent to a granulator for solidification and granulation. The granular material obtained after drying is the reference MBBR filler composition.

[0094] Comparative Example 2

[0095] Preparation of reference MBBR filler composition: 100 parts of polypropylene, 6 parts of maleic anhydride grafted polyolefin, 1 part of antioxidant (antioxidant 1010), 1 part of ultraviolet resistant agent (ultraviolet absorber 1130) and 25 parts of inorganic filler (silicon dioxide) were weighed into a dispersion mixing device and mixed uniformly, then sent to a granulator for solidification and granulation. The granular material obtained after drying is the reference MBBR filler composition.

[0096] Test Example Sewage treatment capacity test:

[0097] The sludge was put into the biochemical tank and water was added to make the sludge concentration 1000 mg / L, and then carbon source was added to the biochemical tank to control the COD value at 250 mg / L, and then the biological filler in the examples and the comparative examples was added respectively for static culture, and the air was blown for 2 h, and then static culture was carried out for 2 h, and then the air was blown for 2 h, and then static culture was carried out for 2 h, and the operation was repeated until the thickness of the biofilm on the surface of the filler reached 0.5 mm, and the biofilm formation and start-up were completed. Then the artificial prepared simulated domestic sewage was introduced, the water temperature was controlled at 25℃, the influent NH4 + -N concentration was about 35 mg / L, TN concentration was about 45 mg / L, TP concentration was about 15 mg / L, and the dissolved oxygen concentration was 7-8 mg / L. The TN, NH3-N and TP concentrations after 24 h, 10 d and 20 d of normal operation after the biofilm formation was completed were calculated, and the results are shown in Table 1.

[0098] Table 1

[0099]

[0100] From the above results, it can be seen that the anthraquinone modified pyrite prepared by the present application has good oxidation resistance, and is not easy to be oxidized in the process of denitrification and phosphorus removal. Therefore, the MBBR filler composition prepared from the anthraquinone modified pyrite, polyolefin and other raw materials has high denitrification and phosphorus removal effect and good running stability in the wastewater treatment process.

[0101] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application without departing from the principles and purposes of the present application.

Claims

1. A method for preparing anthraquinone-modified pyrite, characterized in that: The preparation method of the anthraquinone-modified pyrite comprises polymerizing carbon-carbon double bond-modified pyrite, an anthraquinone-containing polymerizable monomer, and other polymerizable monomers to obtain the anthraquinone-modified pyrite; the carbon-carbon double bond-modified pyrite is obtained by surface-modifying the pyrite with an alkenyl silane coupling agent; the anthraquinone-containing polymerizable monomer has a structure shown in formula (1); In formula (1), R1 is -O- or -NH-, and R2 is H, hydroxyl, amino, amino derivative or C1-C5 alkyl; The other polymerizable monomer has a structure shown in formula (2): In formula (2), R3 is -NH2 or -OR4, and R4 is H or a C1-C5 alkyl group.

2. The method for preparing anthraquinone-modified pyrite according to claim 1, wherein The mass ratio of the carbon-carbon double bond modified pyrite, the anthraquinone-containing polymerizable monomer and the other polymerizable monomers is 1:(0.03-0.5):(0.05-0.2).

3. The method for preparing anthraquinone-modified pyrite according to claim 1, wherein The average particle size of the pyrite is 1 to 100 μm.

4. The method for preparing anthraquinone-modified pyrite according to claim 1, wherein The other polymerizable monomer is selected from at least one of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylamide, methyl acrylate and ethyl acrylate.

5. The method for preparing anthraquinone-modified pyrite according to claim 1, wherein The polymerization reaction is carried out in water or an organic solvent.

6. The method for preparing anthraquinone-modified pyrite according to claim 5, wherein: When the solvent is water, a surfactant is also added.

7. The method for preparing anthraquinone-modified pyrite according to claim 1, wherein: The preparation method of the anthraquinone-containing polymerizable monomer comprises the steps of using acrylic acid to perform surface modification on (amino-hydroxy) anthraquinone to obtain an anthraquinone-containing polymerizable monomer having a structure shown in formula (1).

8. Anthraquinone-modified pyrite prepared by the method according to any one of claims 1 to 7.

9. A MBBR filler composition, characterized in that The MBBR filler composition comprises polyolefin, the anthraquinone-modified pyrite according to claim 8, maleic anhydride-grafted polyolefin, an antioxidant, an anti-ultraviolet agent and an inorganic filler.

10. The MBBR filler composition according to claim 9, characterized in that The mass ratio of the polyolefin, anthraquinone-modified pyrite, maleic anhydride-grafted polyolefin, antioxidant, UV inhibitor and inorganic filler is 100:(1-20):(1-10):(0.5-1.5):(0.3-2):(5-50).

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