Polyurethane microsphere modified MBBR filler, and preparation method and application thereof

Abstract

The application belongs to the technical field of MBBR fillers, and particularly relates to polyurethane microsphere modified MBBR fillers, a preparation method thereof and application. The polyurethane microsphere modified MBBR fillers comprise polyolefin and anthraquinone modified polyurethane microspheres with a mass ratio of 100:(3-20). The anthraquinone modified polyurethane microspheres comprise a first block formed by diaminanthraquinone and a second block formed by dihydric alcohol. The polyurethane microspheres with a two-block structure of the first block of diaminanthraquinone and the second block of dihydric alcohol arranged alternately are prepared, so that the polyurethane microspheres can be reacted with polyolefin in a melt processing stage, grafted onto polyolefin and formed into a crosslinked structure, and thus the obtained polyurethane microsphere modified MBBR fillers simultaneously have good mechanical properties, aging resistance and high sewage treatment efficiency.

Description

TECHNICAL FIELD

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

[0002] The moving bed biofilm reactor (MBBR) is a new water treatment process emerging in recent years, which realizes the purification of polluted water bodies through the metabolic action of anaerobic microorganisms and aerobic microorganisms, and is a new and efficient sewage treatment process. In the MBBR treatment process, the filler, as a carrier of microorganisms, is a core component of the biofilm reactor, has an important influence on the types, quantity and activity of microorganisms, and is a key factor determining the load size and sewage purification effect in the sewage treatment process, so it is very important to select a suitable filler for the biofilm reactor. At present, the fillers mainly used in China are honeycomb fillers, three-dimensional corrugated fillers, soft fiber fillers, semi-soft fillers and suspended fillers made of plastic or glass steel, but there are still problems of poor mechanical properties and easy aging. Polyurethane, as a new emerging high polymer material with broad development prospects, has excellent comprehensive properties and wide application, and is one of the fillers commonly used in the MBBR process. The polyurethane microspheres have good chelating capacity, biocompatibility and adsorption due to the microphase structure and porosity of urethane groups, but they also have problems of poor mechanical properties, weak impact resistance, poor aging resistance and low sewage degradation capacity. SUMMARY

[0003] The present application aims at the deficiencies of the polyurethane fillers in the prior art, such as poor mechanical properties, easy aging and low sewage treatment capacity, and provides a MBBR filler with good mechanical properties, aging resistance and high sewage treatment capacity.

[0004] Specifically, the polyurethane microsphere modified MBBR filler comprises polyolefin and anthraquinone modified polyurethane microspheres with a mass ratio of 100:(3-20); the anthraquinone modified polyurethane microspheres comprise a first block formed by diaminanthraquinone and a second block formed by a dihydric alcohol.

[0005] In a preferred embodiment, the first block and the second block of the anthraquinone modified polyurethane microspheres are arranged alternately.

[0006] In a preferred embodiment, the adjacent first block and the second block are connected by a urethane bond.

[0007] In a preferred embodiment, the second block comprises at least a hydrocarbyl dihydric alcohol.

[0008] In a preferred embodiment, the anthraquinone-modified polyurethane microspheres are prepared by the following method:

[0009] S1, condensation reaction of diisocyanate, diaminanthraquinone and dihydric alcohol under the action of a catalyst to obtain an anthraquinone-modified polyurethane prepolymer;

[0010] S2, mixing reaction of the anthraquinone-modified polyurethane prepolymer obtained in step S1 with a polyamine and a dispersing agent to obtain the anthraquinone-modified polyurethane microspheres.

[0011] In a preferred embodiment, the molar ratio of diisocyanate to the sum of the moles of diaminanthraquinone and dihydric alcohol is 1:(0.9-0.95).

[0012] In a preferred embodiment, the molar ratio of diisocyanate, diaminanthraquinone and catalyst is 1:(0.5-0.9):(0.05-0.25).

[0013] In a preferred embodiment, the diisocyanate is at least one selected from isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and dicyclohexylmethane diisocyanate.

[0014] In a preferred embodiment, the diaminanthraquinone is at least one selected from 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone and 1,3-diaminoanthraquinone.

[0015] In a preferred embodiment, the dihydric alcohol comprises at least a hydrocarbyl dihydric alcohol.

[0016] In a preferred embodiment, the dihydric alcohol is a mixture of a hydrocarbyl dihydric alcohol and a polyether dihydric alcohol and / or a polyester dihydric alcohol.

[0017] In a preferred embodiment, the average molecular weight of the polyether dihydric alcohol is 400-20000.

[0018] In a preferred embodiment, the average molecular weight of the polyester dihydric alcohol is 400-20000.

[0019] In a preferred embodiment, the hydrocarbyl dihydric alcohol has the general formula HOROH.

[0020] In a preferred embodiment, R is a C 12 -C 36 alkylene group and / or a C4-C 24 alkenylene group.

[0021] The application provides a preparation method of the polyurethane microsphere modified MBBR filler, which comprises the following steps: mixing, melting, extruding, granulating and injection molding of polyolefin and anthraquinone modified polyurethane microspheres, so that the polyurethane microsphere modified MBBR filler is obtained.

[0022] The application further provides application of the polyurethane microsphere modified MBBR filler in sewage treatment.

[0023] The key of the application is that the anthraquinone modified polyurethane microspheres with a two-block structure of alternating arrangement of a first block of diaminoanthraquinone and a second block of dihydric alcohol are prepared, so that the polyurethane microspheres can be reacted with polyolefin in a melting process stage, grafted onto the polyolefin and formed into a crosslinked structure, and thus the polyurethane microsphere modified MBBR filler obtained can have good mechanical properties, aging resistance and high sewage treatment efficiency. DETAILED DESCRIPTION

[0024] The polyurethane microsphere modified MBBR filler provided by the application comprises polyolefin and anthraquinone modified polyurethane microspheres with a mass ratio of 100:(3-20). The content of the anthraquinone modified polyurethane microspheres is 3-20 parts by weight, for example, 3, 5, 8, 10, 12, 15, 18, 20 parts by weight or any value therebetween, based on 100 parts by weight of the polyolefin.

[0025] In the application, the anthraquinone modified polyurethane microspheres comprise a first block formed of diaminoanthraquinone and a second block formed of dihydric alcohol. Preferably, the second block comprises at least a hydrocarbyl dihydric alcohol. More preferably, the first block and the second block of the anthraquinone modified polyurethane microspheres are arranged alternately. More preferably, the adjacent first block and the second block are connected by a urethane bond.

[0026] In the application, the anthraquinone modified polyurethane microspheres are prepared by the following method:

[0027] S1, performing a condensation reaction on diisocyanate, diaminoanthraquinone and dihydric alcohol under the action of a catalyst to obtain an anthraquinone modified polyurethane prepolymer;

[0028] S2, mixing and reacting the anthraquinone modified polyurethane prepolymer obtained in step S1 with a polyamine and a dispersant to obtain the anthraquinone modified polyurethane microspheres.

[0029] In the preparation process of the anthraquinone modified polyurethane microspheres, in step S1, the condensation reaction can be performed by polymerizing diisocyanate and diaminoanthraquinone under the action of a catalyst to obtain a primary polymer, and then performing a chain extension reaction on the obtained primary polymer and dihydric alcohol to obtain the anthraquinone modified polyurethane prepolymer.

[0030] In the preparation process of the anthraquinone-modified polyurethane microspheres, in step S1, the polymerization reaction conditions include a temperature preferably 50-70℃, such as 50℃, 52℃, 55℃, 58℃, 60℃, 62℃, 65℃, 68℃, 70℃, or any value between them; and a time preferably 2-5h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or any value between them.

[0031] In the preparation process of the anthraquinone-modified polyurethane microspheres, in step S1, the chain extension reaction conditions include a temperature preferably 70-100℃, such as 70℃, 72℃, 75℃, 78℃, 80℃, 82℃, 85℃, 88℃, 90℃, 92℃, 95℃, 98℃, 100℃, or any value between them; and a time preferably 2-3h, such as 2h, 2.2h, 2.5h, 2.8h, 3h, or any value between them.

[0032] In the preparation process of the anthraquinone-modified polyurethane microspheres, in step S2, the mixing reaction conditions include a temperature preferably 40-60℃, such as 40℃, 42℃, 45℃, 48℃, 50℃, 52℃, 55℃, 58℃, 60℃, or any value between them; and a time preferably 0.5-1.5h, such as 0.5h, 0.8h, 1.0h, 1.2h, 1.5h, or any value between them.

[0033] In the present application, the molar ratio of the diisocyanate, the diaminoanthraquinone, and the catalyst is preferably 1:(0.5-0.9):(0.05-0.25). Taking the molar amount of the diisocyanate monomer as 1 mol, the molar amount of the diaminoanthraquinone is 0.5-0.9 mol, such as 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, 0.9 mol, or any value between them; and the molar amount of the catalyst is 0.05-0.25 mol, such as 0.05 mol, 0.08 mol, 0.1 mol, 0.12 mol, 0.15 mol, 0.18 mol, 0.2 mol, 0.22 mol, 0.25 mol, or any value between them.

[0034] In the present application, the ratio of the molar number of the diisocyanate to the sum of the molar numbers of the diaminoanthraquinone and the dihydric alcohol is 1:(0.9-0.95), such as 1:0.9, 1:0.91, 1:0.92, 1:0.93, 1:0.94, 1:0.95, or any value between them.

[0035] In the present application, specific examples of the diisocyanate include, but are not limited to, at least one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and dicyclohexylmethane diisocyanate.

[0036] In the present application, specific examples of the diaminoanthraquinone include, but are not limited to, at least one of 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, and 1,3-diaminoanthraquinone.

[0037] In the present application, the catalyst is selected from the group consisting of an organotin-based catalyst and / or an amine-based catalyst. Specific examples of the organotin-based catalyst include, but are not limited to, at least one of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, and octyltin oxide. Specific examples of the amine-based catalyst include, but are not limited to, at least one of triethylamine, triethanolamine, diethylenetriamine, N,N-dimethylcyclohexylamine, N,N'-dimethylpyridine, N,N-dimethylbenzylamine, diethylenetriamine, and triethylenetetramine.

[0038] In the present application, the diol includes at least a hydrocarbyl diol having a general formula of HOROH. Preferably, the R is a C 12 ~C 36 alkylene group and / or a C4~C 24 alkenylene group. Specific examples of the C 12 ~C 36 alkylene group include, but are not limited to, at least one of dodecylene, hexadecylene, heptadecylene, octadecylene, tetracosylene, and triacontylene. Specific examples of the C4~C 24 alkenylene group include, but are not limited to, at least one of butenylene, pentenylene, hexenylene, heptenylene, octenylene, dodecenylene, and hexadecenylene.

[0039] In the present application, the diol is a mixture of a hydrocarbyl diol and a polyether diol and / or a polyester diol. The polyether diol is selected from at least one of polyethylene glycol, polypropylene glycol, and polytetrahydrofuran. The polyester diol is selected from at least one of polycaprolactone diol, polyethylene adipate, and polybutylene adipate.

[0040] In the present application, the average molecular weight of the polyether diol is preferably 400 to 20,000 g / mol, such as 400 g / mol, 800 g / mol, 1,000 g / mol, 2,000 g / mol, 3,000 g / mol, 4,000 g / mol, 5,000 g / mol, 6,000 g / mol, 7,000 g / mol, 8,000 g / mol, 9,000 g / mol, 10,000 g / mol, 12,000 g / mol, 15,000 g / mol, 18,000 g / mol, 20,000 g / mol, or any value therebetween. The average molecular weight of the polyester diol is preferably 400 to 20,000 g / mol, such as 400 g / mol, 800 g / mol, 1,000 g / mol, 2,000 g / mol, 5,000 g / mol, 8,000 g / mol, 10,000 g / mol, 12,000 g / mol, 15,000 g / mol, 18,000 g / mol, 20,000 g / mol, or any value therebetween.

[0041] In the present application, the polyamine is an amine having three or more amino groups in the molecule, and can be specifically at least one of hexamethylenetetramine, diethylenetriamine, and diethylenetriamine. The amount of the polyamine added is such that the concentration of the solution thereof is 0.05 to 1%, such as 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, or any value therebetween.

[0042] In the present application, the dispersant is polyvinylpyrrolidone. The amount of the dispersant added is such that the concentration of the solution thereof is 1 to 3%, such as 1%, 1.2%, 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8%, 3.0%, or any value therebetween.

[0043] In the present application, the polyolefin is a homopolymer and / or a copolymer. Preferably, specific examples of the polyolefin include, but are not limited to, at least one of polyethylene, polypropylene, polybutylene, polyamylene, polyhexylene, polyoctylene, and poly(4-methyl-1-pentene).

[0044] In the present application, the average molecular weight of the polyolefin is 500 to 5,000 g / mol, such as 500 g / mol, 800 g / mol, 1,000 g / mol, 1,500 g / mol, 2,000 g / mol, 2,500 g / mol, 3,000 g / mol, 3,500 g / mol, 4,000 g / mol, 4,500 g / mol, 5,000 g / mol, or any value therebetween.

[0045] The application provides a preparation method of polyurethane microsphere modified MBBR filler, which comprises the following steps: mixing, melting, extruding, granulating and injection molding of polyolefin and anthraquinone modified polyurethane microspheres, so as to obtain the polyurethane microsphere modified MBBR filler.

[0046] In addition, the application further provides application of the polyurethane microsphere modified MBBR filler in sewage treatment.

[0047] The application will be described in detail through specific examples.

[0048] In the following examples and comparative examples, the parts of raw materials refer to weight parts.

[0049] Preparation of anthraquinone modified polyurethane microspheres

[0050] S1, 17.87g (0.075mol) of 1,4-diaminoanthraquinone and 16.82g (0.1mol) of hexamethylene diisocyanate are weighed into a reaction bottle under the protection of nitrogen, vacuumized for 40min at room temperature, then 1.52g (0.015mol) of triethylamine is added dropwise under the protection of nitrogen while stirring, and the initial polymer is obtained after continuous reaction at 60℃ for 3h;

[0051] S2, 50g (0.01mol) of polyethylene glycol (M n = 5000g / mol) and 1.16g (0.01mol) of 3-hexene-1,6-diol are vacuumized at 80℃ for 1h, then the initial polymer obtained in step S1 is added under the protection of nitrogen, and the anthraquinone modified polyurethane prepolymer is obtained after continuous reaction at 85℃ for 2.5h;

[0052] S3, a proper amount of hexamethylenetetramine and polyvinylpyrrolidone (PVP) are dissolved in deionized water (the concentration of hexamethylenetetramine is 0.08%, and the concentration of PVP is 2%), heated to 50℃ while stirring, the anthraquinone modified polyurethane prepolymer obtained in step S2 is added dropwise at the same time, the dropping time is 30min, then the reaction is continuously carried out for 1h, and the temperature is continuously increased to 80℃ and kept constant until the solvent is completely volatilized; the obtained product is washed with deionized water for three times and dried, so as to obtain the anthraquinone modified polyurethane microspheres.

[0053] Preparation of anthraquinone modified polyurethane microspheres

[0054] S1, 11.9g (0.05mol) of 1,4-diaminoanthraquinone and 16.82g (0.1mol) of hexamethylene diisocyanate are weighed into a reaction bottle under the protection of nitrogen, vacuumized for 40min at room temperature, then 0.51g (0.005mol) of triethylamine is added dropwise under the protection of nitrogen while stirring, and the initial polymer is obtained after continuous reaction at 60℃ for 3h;

[0055] S2, 50 g (0.01 mol) of polyethylene glycol (M n = 5000 g / mol) and 3.48 g (0.03 mol) of 3-hexene-1,6-diol were vacuumed at 80 °C for 1 h, then the obtained prepolymer of step S1 was added under the protection of nitrogen, after continuous reaction at 85 °C for 2.5 h, an anthraquinone modified polyurethane prepolymer was obtained;

[0056] S3, an appropriate amount of hexamethylenetetramine and polyvinylpyrrolidone (PVP) were dissolved in deionized water (the concentration of hexamethylenetetramine was 0.05%, and the concentration of PVP was 3%), while stirring, the temperature was raised to 50 °C, at the same time, the anthraquinone modified polyurethane prepolymer obtained in step S2 was added dropwise, the dropwise adding time was 30 min, then the reaction was continued for 1 h, the temperature was continuously raised to 80 °C and kept constant until the solvent was completely volatilized; the obtained product was washed with deionized water for three times and then dried, thus an anthraquinone modified polyurethane microsphere was obtained.

[0057] Preparation of anthraquinone modified polyurethane microspheres

[0058] S1, 20.25 g (0.085 mol) of 1,4-diaminoanthraquinone and 16.82 g (0.1 mol) of hexamethylene diisocyanate were added into a reaction bottle under the protection of nitrogen, vacuumed at room temperature for 40 min, then 2.53 g (0.025 mol) of triethylamine was added dropwise while stirring under the protection of nitrogen, after continuous reaction at 60 °C for 3 h, a prepolymer was obtained;

[0059] S2, 25 g (0.005 mol) of polycaprolactone diol (M n = 5000 g / mol) and 0.58 g (0.005 mol) of 3-hexene-1,6-diol were vacuumed at 80 °C for 1 h, then the obtained prepolymer of step S1 was added under the protection of nitrogen, after continuous reaction at 85 °C for 2.5 h, an anthraquinone modified polyurethane prepolymer was obtained;

[0060] S3, an appropriate amount of hexamethylenetetramine and polyvinylpyrrolidone (PVP) were dissolved in deionized water (the concentration of hexamethylenetetramine was 0.1%, and the concentration of PVP was 1%), while stirring, the temperature was raised to 50 °C, at the same time, the anthraquinone modified polyurethane prepolymer obtained in step S2 was added dropwise, the dropwise adding time was 30 min, then the reaction was continued for 1 h, the temperature was continuously raised to 80 °C and kept constant until the solvent was completely volatilized; the obtained product was washed with deionized water for three times and then dried, thus an anthraquinone modified polyurethane microsphere was obtained.

[0061] Preparation of reference polyurethane microspheres

[0062] Reference polyurethane microspheres were prepared according to the method of Preparation Example 1, except that 1,4-diaminoanthraquinone was replaced by the same number of moles of ethylenediamine, and the other conditions were the same as in Example 1, and the specific steps were as follows:

[0063] S1, 5.86 g (0.075 mol) of ethylenediamine and 16.82 g (0.1 mol) of hexamethylene diisocyanate were weighed into a reaction bottle under nitrogen protection, vacuumed at room temperature for 40 min, and then 1.52 g (0.015 mol) of triethylamine was added dropwise under nitrogen protection while stirring, and after continuous reaction at 60°C for 3 h, a prepolymer was obtained;

[0064] S2, 50 g (0.01 mol) of polyethylene glycol (M n = 5000 g / mol) and 1.16 g (0.01 mol) of 3-hexene-1,6-diol were vacuumed at 80°C for 1 h, and then the prepolymer obtained in step S1 was added under nitrogen protection, and after continuous reaction at 85°C for 2.5 h, an ethylenediamine-modified polyurethane prepolymer was obtained;

[0065] S3, an appropriate amount of hexamethylenetetramine and polyvinylpyrrolidone (PVP) were dissolved in deionized water (the concentration of hexamethylenetetramine was 0.08%, and the concentration of PVP was 2%), and the temperature was raised to 50°C while stirring, and the ethylenediamine-modified polyurethane prepolymer obtained in step S2 was added dropwise, the dropwise addition time was 30 min, and then the reaction was continued for 1 h, and the temperature was further raised to 80°C and kept constant until the solvent was completely volatilized; the obtained product was washed with deionized water three times and then dried, to obtain reference polyurethane microspheres.

[0066] Preparation of polyurethane microsphere-modified MBBR filler in Example 1

[0067] 100 parts of polypropylene (M n = 5000 g / mol) and 4 parts of anthraquinone-modified polyurethane microspheres of Preparation Example 1 were weighed into a dispersion mixing device and mixed uniformly, and then the obtained mixture was heated to a molten state, cut into particles by an extrusion granulator, and then injection molded, to obtain polyurethane microsphere-modified MBBR filler.

[0068] Preparation of polyurethane microsphere-modified MBBR filler in Example 2

[0069] 100 parts of polypropylene (M n = 2500 g / mol) and 12 parts of anthraquinone-modified polyurethane microspheres of Preparation Example 2 were weighed into a dispersion mixing device and mixed uniformly, and then the obtained mixture was heated to a molten state, cut into particles by an extrusion granulator, and then injection molded, to obtain polyurethane microsphere-modified MBBR filler.

[0070] Preparation of polyurethane microsphere-modified MBBR filler in Example 3

[0071] Take 100 parts of polypropylene (M n The anthraquinone modified polyurethane microspheres of Preparation Example 3 were added into a dispersing mixing device and mixed uniformly, and then the obtained mixture was heated to a molten state, cut into particles by an extrusion granulator, and then injection molded to obtain the polyurethane microsphere modified MBBR filler.

[0072] Preparation of reference MBBR filler of Comparative Example 1

[0073] The reference MBBR filler was prepared according to the method of Example 1, except that the anthraquinone modified polyurethane microspheres of Preparation Example 1 were replaced by the same mass fraction of reference polyurethane microspheres of Comparative Preparation Example 1, and the other conditions were the same as those of Example 1, to obtain the reference MBBR filler.

[0074] Test Example

[0075] (1) Mechanical property test

[0076] A, tensile strength test: the sample to be tested was prepared into a II dumbbell-shaped sample according to the standard of ASTM D638-08, and a universal testing machine was used to break the sample, the tensile rate was 5 mm / min, the tensile strength was tested, and the results are shown in Table 1.

[0077] B, compressive strength test: the sample to be tested was prepared into a II dumbbell-shaped sample according to the standard of ASTM D638-08, and a universal testing machine was used to extrude the sample, the extrusion rate was 5 mm / min, the compressive strength was tested, and the results are shown in Table 1.

[0078] C, wear resistance test: 3M662XW diamond sandpaper was used to sand the surface of the sample to be tested back and forth for 100 times, the mass change was tested, the wear rate was calculated, and the results are shown in Table 1.

[0079] (2) Aging resistance test: the tensile strength, compressive strength and wear resistance of the sample to be tested were tested after being immersed in artificially prepared simulated domestic sewage (COD concentration about 300 mg / L, NH4 + -N concentration about 35 mg / L, TN concentration about 45 mg / L) for 7 days, and the results are shown in Table 1.

[0080] (3) Sewage treatment capacity test:

[0081] 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 fillers in the examples and the comparative examples were added respectively for static culture, and the fillers were blown for 2 h, and then were static for 2 h, and then were blown for 2 h, and then were static for 2 h, and the operation was repeated until the thickness of the biofilm on the surface of the fillers 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 COD concentration was about 350 mg / L, the NH4 + -N concentration was about 35 mg / L, the TN concentration was about 45 mg / L, the dissolved oxygen concentration was 7-8 mg / L, and the removal rates of COD, TN and NH3-N after the biofilm formation was completed and after the normal operation for 24 h were calculated, and the results are shown in Table 2.

[0082] Table 1

[0083]

[0084] Table 2

[0085] No. COD (%) NH4 + -N(%)]]> TN (%) Example 1 90.3 86.5 85.9 Example 2 94.7 90.1 89.6 Example 3 92.7 88.8 87.4 Comparative Example 1 82.4 75.4 74.3 Comparative Example 2 86.5 79.3 78.1

[0086] From the above results, it can be seen that the polyurethane microsphere modified MBBR filler prepared by using the anthraquinone modified polyurethane microspheres with a two-block structure of a diaminoanthraquinone block and a dihydric alcohol block and polyolefin as raw materials has good mechanical properties, and the mechanical properties do not change too much after aging treatment, which further indicates that it has good aging resistance. In addition, the use of polyurethane microspheres and polyolefins in combination is conducive to the growth of microorganisms into a film on the fillers and the film is not easy to fall off, thereby improving the sewage treatment capacity and effect.

[0087] 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 without departing from the principles and purposes of the present application within the scope of the present application.

Claims

1. A polyurethane microsphere modified MBBR media, characterized in that, The polyurethane microsphere modified MBBR filler comprises polyolefin and anthraquinone modified polyurethane microspheres with a mass ratio of 100:(3-20); the anthraquinone modified polyurethane microspheres comprise a first block formed by diaminianthraquinone and a second block formed by a dihydric alcohol; the second block comprises at least a hydrocarbyl dihydric alcohol; the hydrocarbyl dihydric alcohol has a general formula of HOROH, R is a C4-C 24 alkenylene group.

2. The polyurethane microsphere modified MBBR media according to claim 1, characterized in that, The first blocks and the second blocks of the anthraquinone-modified polyurethane microspheres are arranged alternately.

3. The polyurethane microsphere modified MBBR media according to claim 1, characterized in that, The adjacent first blocks and the second blocks are connected by urethane bonds.

4. The polyurethane microsphere modified MBBR media according to claim 1, characterized in that, The anthraquinone-modified polyurethane microspheres are prepared by the following method: S1, diisocyanate, diaminoanthraquinone and dihydric alcohol are subjected to condensation reaction under the action of a catalyst to obtain an anthraquinone-modified polyurethane prepolymer; S2, the anthraquinone-modified polyurethane prepolymer obtained in step S1 is mixed and reacted with a polyamine and a dispersing agent to obtain the anthraquinone-modified polyurethane microspheres.

5. The polyurethane microsphere modified MBBR media according to claim 4, characterized in that, The ratio of the moles of the diisocyanate to the sum of the moles of the diaminoanthraquinone and the dihydric alcohol is 1:(0.9-0.95); the molar ratio of the diisocyanate, the diaminoanthraquinone and the catalyst is 1:(0.5-0.9):(0.05-0.25).

6. The polyurethane microsphere modified MBBR media according to claim 4, characterized in that, The diisocyanate is at least one selected from isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and dicyclohexylmethane diisocyanate.

7. The polyurethane microsphere modified MBBR media according to claim 4, characterized in that, The diaminoanthraquinone is at least one selected from 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone and 1,3-diaminoanthraquinone.

8. The polyurethane microsphere modified MBBR media according to claim 4, characterized in that, The dihydric alcohol at least includes a hydrocarbyl dihydric alcohol.

9. The polyurethane microsphere modified MBBR media according to claim 8, characterized in that, The dihydric alcohol is a mixture of a hydrocarbyl dihydric alcohol, a polyether dihydric alcohol and / or a polyester dihydric alcohol.

10. The polyurethane microsphere modified MBBR media according to claim 9, characterized in that, The average molecular weight of the polyether dihydric alcohol is 400-20,000; the average molecular weight of the polyester dihydric alcohol is 400-20,000.

11. The method for preparing polyurethane microsphere-modified MBBR filler according to any one of claims 1 to 10, characterized in that, The method comprises mixing, melting, extruding, granulating and injection molding of the polyolefin and the anthraquinone-modified polyurethane microspheres to obtain the polyurethane microsphere-modified MBBR filler.

12. Application of the polyurethane microsphere-modified MBBR filler in sewage treatment according to any one of claims 1-10.

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