CN109399788B - Modification method of polyurethane sponge filler and hydrophilic polyurethane sponge filler obtained by modification - Google Patents
Modification method of polyurethane sponge filler and hydrophilic polyurethane sponge filler obtained by modification Download PDFInfo
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- CN109399788B CN109399788B CN201811038738.1A CN201811038738A CN109399788B CN 109399788 B CN109399788 B CN 109399788B CN 201811038738 A CN201811038738 A CN 201811038738A CN 109399788 B CN109399788 B CN 109399788B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
A hydrophilic modification method of polyurethane sponge filler comprises the following steps: (1) cutting the polyurethane sponge filler into blocks, and soaking in a mixed solution of neutral red, nitrite and acid; (2) after soaking treatment, completely soaking the polyurethane sponge filler into deionized water for ultrasonic treatment; (3) soaking in a hydrophilic reagent in stirring after the ultrasonic treatment is finished; (4) and finally, cleaning in the deionized water in stirring. The polyurethane sponge filler can be directly modified, the operation is simple and rapid, and the cost is low; the modification process does not affect other physical and chemical properties of the polyurethane sponge filler, and can be efficiently completed; compared with other modification processes, the method has the advantages of short required time and low energy consumption.
Description
Technical Field
The invention relates to the field of sewage treatment auxiliary materials, in particular to a method for modifying a polyurethane sponge filler and a hydrophilic polyurethane sponge filler obtained by modification.
Background
The suspended filler of the aeration tank by the activated sludge method used in the sewage treatment process is an important carrier of aerobic microorganisms, and the biomass and the performance of the suspended filler directly influence the quality of effluent water. For example, the chinese patent application with publication number CN103951043A discloses a suspended filler for sewage treatment, which is entirely spherical, has a modified coating on the surface, has a diameter of 10-60 mm, and comprises filler pieces and filler cores, wherein the filler pieces are semicircular thin sheets, the filler cores are hollow spheres, the filler pieces are symmetrically and radially arranged in a three-dimensional space around the filler cores, the filler pieces and the filler cores are concentrically arranged, and the inner diameters of the filler pieces are equal to the outer diameters of the filler cores, and the suspended filler is easy to form a film; and the filler core is hollow, and the filler is easy to suspend after film formation.
In the biomembrane process wastewater treatment, compared with other similar materials, the polyurethane sponge filler can realize good separation from water while keeping enough thallus quantity, has higher specific surface area, good space for the attachment and growth of active bacteria in the interior and porosity of more than 97 percent, and is an ideal activated sludge suspension filler.
For example, the Chinese utility model patent with the publication of CN201737772U discloses a suspension polyurethane foam sponge filler for water treatment, which is provided with a filler body, and is characterized in that the filler body is a cube, the length, width and height of the filler body are respectively 5-2mm, the filler body is made of polyurethane foam sponge material, dense micropores are arranged inside and outside the filler body and on the surface of the filler body, the diameter of the micropores is 0.1-1.5mm, and the distance between the micropores is 0.3-3 mm. The utility model is suitable for a suspension filler that uses in the sewage treatment pond, especially is used for the polyurethane foam sponge filler in the activated sludge process aeration tank.
However, since the biofilm formation of the polyurethane sponge filler is achieved only by physical adsorption between the foam and the microorganism, the immobilized microorganism cells are easily exfoliated, which results in a reduction in the treatment effect. Therefore, the polyurethane foam plastic filler needs to be modified, and the purpose is to increase the surface roughness, improve the surface polarity, improve the surface hydrophilic property, increase the number of chemical active groups, increase the film forming speed and the film biomass, and improve the wastewater treatment efficiency.
Disclosure of Invention
The invention provides a method for modifying a polyurethane sponge filler, which is simple to operate and has an obvious modification effect.
A hydrophilic modification method of polyurethane sponge filler comprises the following steps:
(1) cutting the polyurethane sponge filler into blocks, and soaking in a mixed solution of neutral red, nitrite and acid;
(2) after soaking treatment, completely soaking the polyurethane sponge filler into deionized water for ultrasonic treatment;
(3) soaking in a hydrophilic reagent in stirring after the ultrasonic treatment is finished;
(4) and finally, cleaning in the deionized water in stirring.
The working principle of the invention is as follows: in the soaking of the neutral red solution, the electronegativity of the material surface can be improved. Therefore, under the action of the neutral red solution, the electrical property of the surface of the polyurethane sponge filler is changed, so that the hydrophilicity of the whole reaction system is enhanced.
Based on the principle, the polyurethane sponge filler is cut into blocks, soaked in a mixed solution containing neutral red solution, nitrite and acid for a period of time, modified, and completely soaked in deionized water for ultrasonic treatment.
Preferably, in the step (1), the polyurethane sponge filler is cut into blocks with a horizontal projection area of 100-400 square millimeters and a height of 10-20 millimeters. Preferably, the porosity PPI of the polyurethane sponge filler is 10-40, further preferably, the porosity PPI of the polyurethane sponge filler is 10-20, and most preferably 10. Porosity PPI (Pores Per Linear inc.) refers to the average number of Pores Per Inch of length.
Preferably, the concentration of neutral red in the mixed solution is (0.08-0.2) × PPI mol/L; the nitrite concentration is (0.08-0.2) PPI mol/L; the acid concentration is (0.02-0.07) PPI mol/L.
Preferably, the concentration of the neutral red solution in the mixed solution is (0.08-0.2) × PPI mol/L, the concentration of the neutral red solution is in positive correlation with the porosity of the polyurethane sponge filler, and the higher the porosity is, the higher the concentration of the solution is required to be. Below this concentration, the filler electrical change is essentially ineffective; above this concentration, the electrical change value tends to be constant, and is of no practical significance. Further preferably, the concentration of the neutral red solution is (0.08-0.1) × PPI mol/L; most preferably, the concentration of the neutral red solution is 0.1 PPI mol/L.
Preferably, the concentration of the nitrite solution in the mixed solution is (0.08-0.2) × PPI mol/L, and the nitrite is sodium nitrite and potassium nitrite. The concentration of nitrite solution is in positive correlation with the porosity of polyurethane sponge filler, and the higher the porosity is, the higher the required solution concentration is. The ratio of the concentration of sulfite to the concentration of neutral red solution was kept constant at 1: 1. Below this concentration, the filler electrical change is essentially ineffective; above this concentration, the electrical change value tends to be constant, and is of no practical significance. Further preferably, the nitrite concentration is (0.08-0.1) PPI mol/L; most preferably, a sodium nitrite solution with a concentration of 0.1 x PPI mol/L is used.
Preferably, the acid solution in the mixed solution is selected from (0.02-0.07) × PPI mol/L, and the acid solution is hydrochloric acid, sulfuric acid or nitric acid. The concentration of the acidic solution is too low, the pH value is too high, the electrical property change effect is not obvious, the concentration of the acidic solution is too high, and the diazonium reaction cannot occur when the pH value is too low. Further preferably, the acid concentration in the mixed solution is (0.02-0.05) × PPI mol/L; most preferably, the hydrochloric acid solution is at a concentration of 0.05 x PPI mol/L.
The polyurethane sponge filler is soaked in the mixed solution for a period of time for modification treatment, so that the electrical property of the filler is fully and comprehensively modified.
Preferably, the polyurethane sponge filler is soaked in the mixed solution for 3-9 PPI minutes, the soaking time is in positive correlation with the porosity of the polyurethane sponge filler, and the soaking time is longer when the porosity is higher. If the soaking time is too short, the modification effect is not obvious, if the soaking time is too long, the modification effect tends to be constant, and further preferably, the soaking time is (3-6) × PPI minutes; most preferably, the soaking time is 6 x PPI minutes.
Preferably, the modified polyurethane sponge filler is subjected to ultrasonic treatment (0.3-0.8) PPI minutes at the ultrasonic frequency of 60-120 kHz, the cleaning time is too short, and the cleaning effect is not ideal; over time, the modification effect of the polyurethane sponge filler is reduced. Further preferably, the ultrasound frequency is 100kHz and the wash time is 0.5 PPI minutes.
The second working principle of the invention is as follows: the material is changed from hydrophobicity to hydrophilicity under the action of the hydrophilic agent.
Preferably, the hydrophilic agent is cetyl trimethyl quaternary ammonium bromide (CATB), octadecyl dimethyl benzyl quaternary ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, dioctadecyl dimethyl ammonium bromide, and more preferably, the hydrophilic agent is cetyl trimethyl quaternary ammonium bromide (CATB).
Preferably, the concentration of the hydrophilic agent is (0.1-0.3) × PPI mol/L, the polyurethane sponge filler cannot be completely modified due to the low concentration, and the waste of resources is caused due to the high concentration. Further preferably, the concentration of the hydrophilic agent is (0.1-0.2) × PPI mol/L, most preferably, the concentration of the hydrophilic agent is 0.2 × PPI mol/L, the stirring rotating speed is 800-1200 rmp, the rotating speed is too slow, the reaction modification is not obvious, the filler is suspended due to too fast rotating speed, the CATB solution is easy to lose, and the effect with the polyurethane sponge filling cannot be well realized. Further preferably, the rotation speed is 1000 rmp.
Preferably, the polyurethane sponge filler is soaked in the hydrophilic solution for 5-10 minutes, the filler modification effect cannot be achieved due to too short soaking time, and energy waste can be caused due to too long soaking time. Further preferably, the soaking time is 5-8 minutes; most preferably, the soaking time is 8 minutes.
The soaked polyurethane sponge filler needs to be washed by deionized water in stirring.
Preferably, the stirring frequency of the deionized water is 800-1200 rmp, and if the rotation frequency is too low, the cleaning is insufficient, and if the rotation frequency is too high, the modification effect is reduced. Further preferably, the stirring frequency is 1000 rmp.
Preferably, the time of each cleaning is (0.3-0.8) × PPI minutes, insufficient cleaning can result in insignificant modification effect, and cleaning transition can result in energy waste. Further preferably, the wash time is 0.5 PPI minutes.
The invention also provides the polyurethane sponge foam modified by the hydrophilic modification method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyurethane sponge filler can be directly modified, the operation is simple and rapid, and the cost is low;
(2) the modification process does not influence other physical and chemical properties of the polyurethane sponge filler, and can be efficiently finished;
(3) compared with other modification processes, the method has the advantages of short required time and low energy consumption.
Drawings
FIG. 1 is a contact angle before modification
FIG. 2 is the contact angle after modification
The contact angle refers to the included angle at the interface of liquid-solid-gas triple intersection. Contact angles less than 90 degrees are referred to as hydrophilic, less than 5 degrees as superhydrophilic, contact angles greater than 90 degrees are referred to as hydrophobic, and greater than 150 degrees are referred to as superhydrophobic.
Detailed Description
Cutting the polyurethane sponge filler into blocks, wherein the projection area is 100-400 square millimeters, the height is 10-20 millimeters, soaking the polyurethane sponge filler in a mixed solution of neutral red, nitrite and acid for a period of time to change the electronegativity of the polyurethane sponge filler, modifying the polyurethane sponge filler, and completely soaking the polyurethane sponge filler in deionized water for ultrasonic treatment;
soaking in CTAB solution while stirring, changing hydrophobicity of the treated polyurethane sponge filler into hydrophilicity, and cleaning in deionized water while stirring.
Example 1
In this example, a polyurethane sponge filler (porosity PPI is 10) was used as a test object, and a polyurethane sponge filler with an L × B × H ═ 10 × 10 × 10mm was selected, and the electrical property before treatment was-300 and the contact angle was 100 °. Soaking in a mixed solution of 0.8mol/L neutral red solution, 0.8mol/L sodium nitrite solution and 0.2mol/L hydrochloric acid solution for 30 minutes, and cleaning in deionized water with ultrasonic frequency of 100kHz for 3 minutes. The electrical property was found to be-100. And soaking the modified polyurethane sponge filler in a CATB solution with the concentration of 1.0mol/L and the rotating speed of 800rmp for 5 minutes, cleaning the modified polyurethane sponge filler with 800rmp deionized water for 2 times, 3 minutes each time, and testing by using a contact angle tester to obtain the polyurethane sponge filler with a contact angle of 5 degrees.
Example 2
In this example, a polyurethane sponge filler (porosity PPI is 10) was used as a test object, and a polyurethane sponge filler with an L × B × H of 12 × 10 × 10mm was selected, where the electrical property before treatment was-300 and the contact angle was 100 °. Soaking in a mixed solution of 1.0mol/L neutral red solution, 1.0mol/L sodium nitrite solution and 0.5mol/L hydrochloric acid solution for 60 minutes, and cleaning in deionized water with ultrasonic frequency of 100kHz for 5 minutes. The measured electrical property was 0. And soaking the modified polyurethane sponge filler in a CATB solution with the concentration of 2.0mol/L and the rotating speed of 1000rmp for 8 minutes, cleaning the modified polyurethane sponge filler with 1000rmp of deionized water for 3 times, each time for 5 minutes, and testing by using a contact angle tester to obtain the polyurethane sponge filler with a contact angle of 0 degree.
Example 3
In this example, a polyurethane sponge filler (porosity PPI is 10) was used as a test object, and a polyurethane sponge filler with an L × B × H of 15 × 10 × 10mm was selected, where the electrical property before treatment was-300 and the contact angle was 100 °. Soaking in a mixed solution of 1.5mol/L neutral red solution, 1.5mol/L sodium nitrite solution and 0.5mol/L hydrochloric acid solution for 90 minutes, and cleaning in deionized water with ultrasonic frequency of 100kHz for 6 minutes. The measured electrical property was 0. And soaking the modified polyurethane sponge filler in a CATB solution with the concentration of 3.0mol/L and the rotating speed of 1000rmp for 10 minutes, then cleaning the modified polyurethane sponge filler with 1000rmp of deionized water for 3 times, each time for 5 minutes, and testing by using a contact angle tester to obtain the polyurethane sponge filler with a contact angle of 4 degrees.
Example 4
In this example, a polyurethane sponge filler (porosity PPI is 10) was used as a test object, and a polyurethane sponge filler having an electrical property of-300 and a contact angle of 100 ° before treatment was selected, where L × B × H is 20 × 10 × 10 cm. Soaking in a mixed solution of neutral red solution of 2mol/L, sodium nitrite solution of 2mol/L and hydrochloric acid solution of 0.7mol/L for 90 minutes, and cleaning in deionized water with ultrasonic frequency of 100kHz for 7 minutes. The measured electrical property was 0. And soaking the modified polyurethane sponge filler in a CATB solution with the concentration of 3.0mol/L and the rotating speed of 1000rmp for 10 minutes, then cleaning the modified polyurethane sponge filler with 1000rmp of deionized water for 3 times, each time for 5 minutes, and testing by using a contact angle tester to obtain the polyurethane sponge filler with the contact angle of 6 degrees.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (4)
1. A hydrophilic modification method of polyurethane sponge filler is characterized by comprising the following steps:
(1) cutting the polyurethane sponge filler into blocks, and soaking in a mixed solution of neutral red, nitrite and acid; the nitrite is sodium nitrite or potassium nitrite; the acid is hydrochloric acid, sulfuric acid or nitric acid; the concentration of neutral red in the mixed solution is (0.08-0.2) PPI mol/L, the concentration of nitrite is (0.08-0.2) PPI mol/L, and the concentration of acid is (0.02-0.07) PPI mol/L; the soaking time is (3-9) PPI minutes;
(2) after soaking treatment, completely soaking the polyurethane sponge filler into deionized water for ultrasonic treatment; the ultrasonic frequency is 60-120 kHz, and the ultrasonic time is (0.3-0.8) PPI minutes;
(3) soaking in a hydrophilic reagent in stirring after the ultrasonic treatment is finished; the hydrophilic reagent is cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate or dioctadecyl dimethyl ammonium bromide; the concentration of the hydrophilic agent is (0.1-0.3) PPI mol/L; the stirring speed is 800-1200 rpm; soaking in a hydrophilic solution for 5-10 minutes;
(4) finally, cleaning in the deionized water in stirring; the stirring frequency is 800-1200 rpm; the time for each washing is (0.3-0.8) PPI minutes.
2. The hydrophilic modification method according to claim 1, wherein the polyurethane sponge filler is cut into blocks having a horizontal projection area of 100 to 400 mm and a height of 10 to 20 mm in step (1).
3. The hydrophilic modification method according to claim 1, wherein the polyurethane sponge filler has a porosity PPI of 10-40.
4. A polyurethane sponge foam modified by the hydrophilic modification method as claimed in any one of claims 1 to 3.
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| CN101735475A (en) * | 2009-12-10 | 2010-06-16 | 清华大学 | Preparation method of hydrophilic polyurethane porous support |
| CN101982427A (en) * | 2010-10-25 | 2011-03-02 | 四川城际轨道交通材料有限责任公司 | Method for modifying composite surface of carbon fiber |
| EP2168975A3 (en) * | 2004-05-24 | 2012-01-11 | Genvault Corporation | Method of stably storing biomolecules in recoverable form |
| CN103221074A (en) * | 2010-10-27 | 2013-07-24 | 拜耳知识产权有限责任公司 | Hydrophilic, aliphatic polyurethane foams |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0739376A (en) * | 1993-08-04 | 1995-02-10 | Kansai Paint Co Ltd | Carrier for immobilizing microbe |
| CN103114038B (en) * | 2007-11-20 | 2015-02-11 | 3M创新有限公司 | Sample cell and kit |
| CN106832087B (en) * | 2017-01-22 | 2018-10-12 | 天津城建大学 | The preparation method and application for the polyacrylic acid hydrogel mediator functional material that dimethyl diaminophenazine chloride is modified |
| CN106833333B (en) * | 2017-02-13 | 2019-10-25 | 江苏丰彩新型建材有限公司 | A kind of aqueous anti-doodling paint and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2168975A3 (en) * | 2004-05-24 | 2012-01-11 | Genvault Corporation | Method of stably storing biomolecules in recoverable form |
| CN101735475A (en) * | 2009-12-10 | 2010-06-16 | 清华大学 | Preparation method of hydrophilic polyurethane porous support |
| CN101982427A (en) * | 2010-10-25 | 2011-03-02 | 四川城际轨道交通材料有限责任公司 | Method for modifying composite surface of carbon fiber |
| CN103221074A (en) * | 2010-10-27 | 2013-07-24 | 拜耳知识产权有限责任公司 | Hydrophilic, aliphatic polyurethane foams |
| CN106552601A (en) * | 2016-10-25 | 2017-04-05 | 昆明理工大学 | Polyurethane foam surface is coupled adsorbing material of gelatin and its preparation method and application |
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