CN110724304B - Modified polyurethane sponge biological filler and preparation method thereof - Google Patents

Modified polyurethane sponge biological filler and preparation method thereof Download PDF

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Publication number
CN110724304B
CN110724304B CN201911213123.2A CN201911213123A CN110724304B CN 110724304 B CN110724304 B CN 110724304B CN 201911213123 A CN201911213123 A CN 201911213123A CN 110724304 B CN110724304 B CN 110724304B
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polyurethane sponge
parts
biological filler
aqueous solution
asparagine
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CN110724304A (en
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赵勇娇
单连斌
王允妹
张磊
魏春飞
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Shenyang Academy Environmental Sciences
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Shenyang Academy Environmental Sciences
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/40Impregnation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/105Characterized by the chemical composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The invention relates to the technical field of sewage treatment, in particular to a modified polyurethane sponge biological filler which comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 200-300 parts of roughening liquid, 20-30 parts of sodium carbonate, 10-20 parts of methyl potassium silicate and 15-25 parts of asparagine, wherein the roughening liquid comprises the following components: 550-650 g/L of sulfuric acid and 250-350 g/L of chromium trioxide. A preparation method of a modified polyurethane sponge biological filler comprises the following steps: s1, cleaning the polyurethane sponge; S2-S3, coarsening; s4, soaking in a methyl potassium silicate aqueous solution; s5, soaking in an asparagine aqueous solution to obtain the modified polyurethane sponge biological filler. The polyurethane sponge is modified to have functional groups, and the polyurethane sponge can act with amino acid residues of microbial peptide chains to form covalent bond combination, so that microbes and enzymes are fixed on the carrier filler, mass propagation of cultured bacteria is facilitated, the biological load is increased, and the sewage treatment effect is improved.

Description

Modified polyurethane sponge biological filler and preparation method thereof
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a modified polyurethane sponge biological filler and a preparation method thereof.
Background
The suspended filler is the core part of the MBBR, and the parameters such as the performance, the filling rate and the like directly influence the treatment effect of the reactor, so that the selection of the proper filler is a key factor for the successful operation of the MBBR. The polyurethane sponge filler is a commonly used filler in an MBBR (moving bed biofilm reactor) and is formed by oxygen and hydrogen dual blasting, and air holes are uniformly communicated with each other, so that the aim of culturing strains in an all-round way by using the whole biological sponge filler can be fulfilled. But the method can only carry out simple physical adsorption on microorganisms, the microorganisms are easy to lose under the shearing of water and gas, the biological capacity is general, and the treatment effect is general.
Therefore, we propose a modified polyurethane sponge biological filler and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a modified polyurethane sponge biological filler and a preparation method thereof.
The modified polyurethane sponge biological filler comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 200-300 parts of roughening liquid, 20-30 parts of sodium carbonate, 10-20 parts of methyl potassium silicate and 15-25 parts of asparagine.
Preferably, the roughening solution comprises the following components: 550-650 g/L of sulfuric acid and 250-350 g/L of chromium trioxide.
A preparation method of a modified polyurethane sponge biological filler comprises the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 10-20S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 20S-30S, taking out, washing with deionized water for 5-10 times, and drying;
s4, soaking the dried polyurethane sponge into 4-8% of methyl potassium silicate aqueous solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into 5% -8% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
Preferably, the roughening temperature is 20 ℃ to 35 ℃.
Preferably, the dipping temperature of the asparagine aqueous solution is 35 ℃ to 45 ℃.
Preferably, the asparagine-containing aqueous solution is prepared by dissolving asparagine-containing aqueous solution in an aqueous solution containing 1 to 2g/L of hydrochloric acid.
The invention has the beneficial effects that:
the polyurethane sponge is modified to have functional groups, and the polyurethane sponge can act with amino acid residues of microbial peptide chains to form covalent bond combination, so that microbes and enzymes are fixed on the carrier filler, mass propagation of cultured bacteria is facilitated, the biological load is increased, and the sewage treatment effect is improved.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The first embodiment is as follows:
the modified polyurethane sponge biological filler comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 250 parts of coarsening liquid, 25 parts of sodium carbonate, 15 parts of methyl potassium silicate and 20 parts of asparagine.
A preparation method of a modified polyurethane sponge biological filler comprises the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 10S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 25S, taking out the polyurethane sponge, washing the polyurethane sponge with deionized water for 10 times, and drying;
s4, soaking the dried polyurethane sponge into 4% methyl potassium silicate water solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into a 5% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
In this example, the roughening solution comprises the following components: 650g/L of sulfuric acid, 250g/L of chromium trioxide, the coarsening temperature of 20 ℃, the dipping temperature of the asparagine aqueous solution of 35 ℃, and when preparing the asparagine aqueous solution, the asparagine aqueous solution is dissolved by adopting hydrochloric acid aqueous solution containing 1.5 g/L.
Example two:
the modified polyurethane sponge biological filler comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 250 parts of coarsening liquid, 25 parts of sodium carbonate, 15 parts of methyl potassium silicate and 20 parts of asparagine.
A preparation method of a modified polyurethane sponge biological filler comprises the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 15S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 25S, taking out the polyurethane sponge, washing the polyurethane sponge with deionized water for 10 times, and drying;
s4, soaking the dried polyurethane sponge into 6% methyl potassium silicate water solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into 6% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
In this example, the roughening solution comprises the following components: 650g/L of sulfuric acid, 250g/L of chromium trioxide, the coarsening temperature of 25 ℃, the dipping temperature of the asparagine aqueous solution of 40 ℃, and when preparing the asparagine aqueous solution, the asparagine aqueous solution is dissolved by adopting hydrochloric acid aqueous solution containing 1.5 g/L.
Example three:
the modified polyurethane sponge biological filler comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 250 parts of coarsening liquid, 25 parts of sodium carbonate, 15 parts of methyl potassium silicate and 20 parts of asparagine.
A preparation method of a modified polyurethane sponge biological filler comprises the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 15S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 25S, taking out the polyurethane sponge, washing the polyurethane sponge with deionized water for 10 times, and drying;
s4, soaking the dried polyurethane sponge into 8% methyl potassium silicate water solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into 6% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
In this example, the roughening solution comprises the following components: 550g/L of sulfuric acid, 350g/L of chromium trioxide, the coarsening temperature of 35 ℃, the dipping temperature of the asparagine aqueous solution of 45 ℃, and when preparing the asparagine aqueous solution, the asparagine aqueous solution is dissolved by hydrochloric acid aqueous solution containing 1.5 g/L.
Example four:
the modified polyurethane sponge biological filler comprises the following raw materials in parts by weight: 100 parts of polyurethane sponge, 250 parts of coarsening liquid, 25 parts of sodium carbonate, 15 parts of methyl potassium silicate and 20 parts of asparagine.
A preparation method of a modified polyurethane sponge biological filler comprises the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 20S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 25S, taking out the polyurethane sponge, washing the polyurethane sponge with deionized water for 10 times, and drying;
s4, soaking the dried polyurethane sponge into 6% methyl potassium silicate water solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into 8% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
In this example, the roughening solution comprises the following components: 550g/L of sulfuric acid, 350g/L of chromium trioxide, the coarsening temperature of 35 ℃, the dipping temperature of the asparagine aqueous solution of 40 ℃, and when preparing the asparagine aqueous solution, the asparagine aqueous solution is dissolved by hydrochloric acid aqueous solution containing 1.5 g/L.
The modified polyurethane sponge biofillers of examples one to five and the polyurethane sponges of the comparative example, which were the polyurethane sponge raw materials before modification, were subjected to daily COD removal tests.
Time (d)/COD removal (%) 1 2 4 6 8
Example one 82 88 90 82 85
Example two 85 88 90 85 82
EXAMPLE III 83 90 93 88 90
Example four 85 87 92 87 92
Comparative example 82 85 80 75 81
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (6)

1. The modified polyurethane sponge biological filler is characterized by comprising the following raw materials in parts by weight: 100 parts of polyurethane sponge, 200-300 parts of roughening liquid, 20-30 parts of sodium carbonate, 10-20 parts of methyl potassium silicate and 15-25 parts of asparagine.
2. The modified polyurethane sponge biological filler as claimed in claim 1, wherein the coarsening liquid comprises the following components: 550-650 g/L of sulfuric acid and 250-350 g/L of chromium trioxide.
3. A preparation method of a modified polyurethane sponge biological filler is characterized by comprising the following steps:
s1, respectively carrying out ultrasonic washing on the polyurethane sponge by using carbon tetrachloride, ethanol and deionized water;
s2, placing the cleaned and dried polyurethane sponge into a roughening solution, roughening for 10-20S, taking out, centrifuging, and removing the roughening solution adsorbed by the polyurethane sponge;
s3, placing the coarsened polyurethane sponge into a 25% sodium carbonate solution to be soaked for 20S-30S, taking out, washing with deionized water for 5-10 times, and drying;
s4, soaking the dried polyurethane sponge into 4-8% of methyl potassium silicate aqueous solution, taking out after 15-20 min, and putting the polyurethane sponge into a vacuum drier for drying to be semi-dry;
s5, placing the semi-dry polyurethane sponge into 5% -8% asparagine aqueous solution, soaking for 45-60 min, taking out, and drying to obtain the modified polyurethane sponge biological filler.
4. The preparation method of the modified polyurethane sponge biological filler as claimed in claim 3, wherein the coarsening temperature is 20-35 ℃.
5. The method for preparing the modified polyurethane sponge biological filler as claimed in claim 3, wherein the dipping temperature of the asparagine aqueous solution is 35-45 ℃.
6. The preparation method of the modified polyurethane sponge biological filler as claimed in claim 3, wherein the asparagine aqueous solution is dissolved by using 1-2 g/L hydrochloric acid aqueous solution.
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CN103627015A (en) * 2012-08-27 2014-03-12 苏州科技学院 Preparation method of hydrophilic polymer-modified polyurethane foaming plastic carrier
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CN108854160A (en) * 2018-06-29 2018-11-23 合肥炫升环保材料科技有限公司 A kind of preparation method of the super-hydrophobic foam of water-oil separating
CN109354165A (en) * 2018-12-03 2019-02-19 巩义市宏盛稀有金属有限公司 A method of using hybrid biosystem integrated treatment sanitary sewage
CN109621923A (en) * 2018-12-13 2019-04-16 沈阳建筑大学 A kind of super-hydrophobic oleophylic sponge material and preparation method thereof and water-oil separating application

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US10543476B2 (en) * 2016-08-04 2020-01-28 The University Of Massachusetts Porous materials, methods of manufacture thereof and articles comprising the same

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CN103627015A (en) * 2012-08-27 2014-03-12 苏州科技学院 Preparation method of hydrophilic polymer-modified polyurethane foaming plastic carrier
CN104591386A (en) * 2014-12-30 2015-05-06 东莞市蓝天碧水环境科技工程有限公司 Method for purifying water quality through efficient ecological packing biological carrier
CN108854160A (en) * 2018-06-29 2018-11-23 合肥炫升环保材料科技有限公司 A kind of preparation method of the super-hydrophobic foam of water-oil separating
CN109354165A (en) * 2018-12-03 2019-02-19 巩义市宏盛稀有金属有限公司 A method of using hybrid biosystem integrated treatment sanitary sewage
CN109621923A (en) * 2018-12-13 2019-04-16 沈阳建筑大学 A kind of super-hydrophobic oleophylic sponge material and preparation method thereof and water-oil separating application

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