CN116199331A - Modification method of polyethylene suspension filler for moving bed biomembrane reactor - Google Patents
Modification method of polyethylene suspension filler for moving bed biomembrane reactor Download PDFInfo
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- CN116199331A CN116199331A CN202310112057.XA CN202310112057A CN116199331A CN 116199331 A CN116199331 A CN 116199331A CN 202310112057 A CN202310112057 A CN 202310112057A CN 116199331 A CN116199331 A CN 116199331A
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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
The invention discloses a modification method of polyethylene suspended filler for a moving bed biomembrane reactor, which uses polyethylene filler as a matrix, treats the surface of the filler by using an acidic potassium dichromate mixed solution, then immerses the filler in a coupling agent (silane coupling agent KH-560, silane coupling agent KH-570 and titanate coupling agent CS-311) aqueous solution, and adds modifier activated carbon powder and gelatin protein to successfully load the activated carbon and the gelatin protein on the surface of the filler. The invention uses the conventional polyethylene filler as a substrate, uses the acidic potassium dichromate mixed solution to treat the surface, and uses the crosslinking reaction of the coupling agent and the macromolecular compound to lead the surface of the filler to be provided with hydrophilic groups such as hydroxyl groups, carbonyl groups and the like, thereby providing favorable conditions for the rapid growth of microorganisms on the surface of the filler and enhancing the film forming effect of the filler. In the sewage treatment process, the packing has better membrane hanging speed, biological membrane quantity, compactness of biological membrane and carrier, and microbial activity than the conventional packing.
Description
Technical Field
The invention belongs to the technical field of sewage biological treatment, and relates to a modification method of polyethylene suspension filler for a Moving Bed Biofilm Reactor (MBBR).
Background
At present, in the traditional sewage treatment technology in China, the biochemical method mainly comprises an activated sludge method and a biomembrane method. Compared with the traditional activated sludge method, the biomembrane method has the advantages of less residual sludge, high treatment efficiency and the like; the MBBR process has the advantages of the traditional fluidized bed and biological contact oxidation method, and becomes a novel efficient sewage treatment method, a certain amount of suspended carriers are added into the reactor, the carriers are in a fluidized state by virtue of the aeration and water flow lifting effects in the reaction tank, and further activated sludge growing in a suspended mode and a biological film growing in an attached mode are formed, so that the moving bed biological film uses the space of the whole reactor, the advantages of the attached phase and the suspended phase organisms are fully exerted, and the advantages and the disadvantages are raised and compensated.
The key of the MBBR technology is that the specific gravity is close to that of water, and the suspended filler which is easy to move freely along with the water under slight stirring has the advantages of large effective specific surface area, suitability for microorganism adsorption growth, strong applicability, wide application range and the like, and can be used for removing organic matters and nitrogen and phosphorus; in addition, the treatment load is high, the occupied area is small, the problems of sludge expansion and sludge backflow are avoided, the impact load is resistant, and the method has a wider application prospect in industrial wastewater treatment.
At present, the variety of suspended fillers produced in the market is various, and the differences of filler materials, structures and performances directly influence the treatment effect of the suspended fillers and also influence the investment cost of sewage treatment to a certain extent.
The polyethylene suspension filler is a common suspension filler in the market, has the advantages of large specific surface area, no toxic action on microorganisms, long service life, low price and the like, and can be applied to the field of water treatment to a certain extent. However, the hydrophilic property and the biocompatibility of the polyethylene filler are poor, the performance of the biological film carrier is poor, the film forming speed is low, the film forming amount is small, the adhesion degree between the biological film and the carrier is low, the microbial activity is poor and the like are solved, and the wide application of the polyethylene filler in sewage treatment is limited to a great extent. Therefore, the hydrophilic polyethylene suspension filler with good microorganism fixing effect and high pollutant treatment efficiency is developed through modification and has very important significance.
Disclosure of Invention
The invention provides a modification method of polyethylene suspension filler for a moving bed biomembrane reactor, which is characterized in that the polyethylene suspension filler in the market is modified by bonding macromolecules by a coupling agent, and the modified filler surface is provided with a certain amount of hydrophilic groups such as hydroxyl groups, carbonyl groups and the like, so that the hydrophilicity is obviously improved. Microorganisms are negatively charged, the surfaces of common fillers are negatively charged, repulsive force is generated between the microorganisms, and the silane coupling agent is used for bonding macromolecules so that the surfaces of modified fillers are positively charged, the microorganisms are opposite to the fillers, and the film forming speed is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the modification method of the polyethylene suspended filler for the moving bed biofilm reactor specifically comprises the following steps:
s1, soaking polyethylene filler in an acidic potassium dichromate solution for 2-4 hours at the temperature of 40-60 ℃, taking out, washing off a brown layer on the surface by water, and draining;
s2, placing the drained polyethylene filler into a phosphoric acid buffer solution for soaking for a period of time, taking out, washing with water, and naturally airing after the leacheate is neutral;
s3, soaking the dried polyethylene filler in a coupling agent hydrolysis solution at the temperature of 25-40 ℃ and stirring for 6-12h, taking out the filler and draining, adding the filler into a mixed solution of powdered activated carbon and gelatin protein, heating to the temperature of 25-40 ℃ and stirring for 18-36h;
s4, taking out the filler, flushing with water, and naturally airing to obtain the polyethylene suspension filler for the moving bed biomembrane reactor.
The preparation method of the modified polyethylene MBBR suspending filler is further improved:
preferably, the acidic potassium dichromate mixed solution is a mixed solution of sulfuric acid and potassium dichromate.
Preferably, the concentration of the potassium dichromate contained in the acidic potassium dichromate mixed solution is 6-8mol/L, and the concentration of the sulfuric acid contained in the acidic potassium dichromate mixed solution is 2-4mol/L.
Preferably, the coupling agent in the coupling agent aqueous solution is one or more than two of silane coupling agent KH-560, silane coupling agent KH-570 and titanate coupling agent CS-311.
Preferably, the preparation method of the coupling agent hydrolysis solution comprises the following steps: mixing coupling agent, ethanol and water according to the mass ratio of 20:72:8, regulating pH to 5.5-6.5, hydrolyzing for 10-20min for later use.
Preferably, the concentration of phosphoric acid in the phosphoric acid buffer solution in the step S2 is 0.01-0.02mol/L, and the soaking time of the polyethylene filler in the phosphoric acid buffer solution is 2-3h.
Preferably, the mixed solution of powdered activated carbon and gelatin protein in step S3 contains 16-32g/L activated carbon and 2-4g/L gelatin protein.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a modification method of polyethylene MBBR (moving bed biofilm reactor) suspended filler, which comprises the following steps:
the method comprises the steps of using polyethylene filler as a matrix, and treating the surface of the filler by using an acidic potassium dichromate mixed solution, wherein the purpose of hydroxylating the surface of the filler is to form a plurality of hydroxyl groups on the surface of the polyethylene matrix so as to carry out dehydration condensation with a silane coupling agent;
the treated polyethylene filler is soaked in phosphoric acid buffer solution for treatment, so that the pH value of the polyethylene filler is regulated to be neutral, and the modified filler is prevented from being added into silane coupling agent solution, so that the silane coupling agent is excessively hydrolyzed.
And (3) immersing the polyethylene filler treated by the phosphoric acid buffer solution in a coupling agent hydrolysis solution, and carrying out surface dehydration reaction on the coupling agent and the filler to increase hydrophilic groups such as hydroxyl, carbonyl and the like.
And then, adding the polyethylene filler into the mixed solution of the activated carbon powder and the gelatin protein, and successfully loading the activated carbon and the gelatin protein on the surface of the filler. The hydrophilic groups such as surface hydroxyl groups and carboxyl groups are increased, the hydrophilicity of the carrier is improved, a large number of attachment sites are provided for microorganism attachment due to the change of surface roughness and charge numbers, and microorganisms represented by nitrifying bacteria are easier to adhere to the surface of the carrier by the principle of opposite phase absorption, so that the formation of a biological film is accelerated, and the film forming speed is improved. Through the adsorption of the activated carbon to the pollutants, the adhesion of microorganisms on the surface of the filler is accelerated, and the gelatin protein is used as the nitrification and denitrification reaction inside the independent filler, so that a carbon source is provided, and the growth and propagation of the microorganisms are better promoted.
2) The invention carries out modification treatment on the conventional polyethylene filler by using a coupling agent, and the modified filler surface is provided with a certain amount of hydrophilic groups such as hydroxyl groups, carbonyl groups and the like, so that the number of positive charges on the surface is obviously increased, and the hydrophilicity is obviously improved. The degradation performance of the filler to pollutants in water can be effectively improved through the synergistic mechanism of the adsorption effect and the microbial degradation effect of the activated carbon attached to the surface of the filler, so that the sewage treatment effect is improved. The great amount of micropores of the activated carbon absorb organic matters and oxygen in the wastewater, a high-concentration nutrition source is provided for the growth and propagation of microorganism groups, enzymes and coenzymes generated in the metabolic process of microorganisms are absorbed and enriched in the micropores of the activated carbon, and the contact time of microorganisms and organic matters on the activated carbon is long, so that the organic matters which are difficult to degrade are possibly decomposed by biological oxidation. In addition, gelatin protein is used as carbon source to supplement by virtue of the adsorption effect of activated carbon, and a large amount of organic matters are attached to the surface of the filler, so that favorable conditions are provided for the rapid growth of microorganisms on the surface of the filler, the film forming speed is further improved, and the film forming effect is enhanced.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
Example 1
The embodiment provides a modification method of polyethylene suspension filler for MBBR (moving bed biofilm reactor), which specifically comprises the following steps:
s1, soaking a cake-shaped polyethylene filler (25 multiplied by 10 mm) in an acidic potassium dichromate solution at 60 ℃ for 3 hours, wherein the acidic potassium dichromate solution is a mixed solution of sulfuric acid and potassium dichromate, the concentration of the potassium dichromate in the mixed solution is 8mol/L, and the concentration of the sulfuric acid is 3mol/L, then taking out the polyethylene filler, washing off a brown layer on the surface by water, and draining;
s2, placing the drained polyethylene filler into a 0.01mol/L phosphoric acid buffer solution for soaking for 2 hours, taking out the polyethylene filler after the solution is neutral, and naturally airing;
s3, mixing a silane coupling agent KH-560, ethanol and water according to a mass ratio of 20:72:8 to prepare a coupling agent hydrolysis solution, wherein the pH value is 6.0, and hydrolyzing for 15min for later use; soaking the polyethylene filler dried in the step S2 in a coupling agent hydrolysis solution at 40 ℃ for 12 hours, stirring, taking out the filler, draining, adding the filler into a mixed solution of powdered activated carbon (the concentration in the mixed solution is 24 g/L) and gelatin protein (the concentration in the mixed solution is 2 g/L), heating to 37 ℃ and stirring for 24 hours;
s4, taking out the filler, flushing with water, and naturally airing to obtain the modified filler for sewage treatment.
The unmodified filler was used as a control and the modified filler was tested separately as follows:
1) Through testing, the surface potential of the polyethylene filler is changed from-20 mV before modification to 140mV after modification.
2) And (3) placing the modified filler in an MBBR reactor for film forming experiments, wherein 7d of the modified filler is marked by wheel insects, clock insects and the like, and the film forming of the unmodified filler can be completed only by 14 d.
Analysis of the modified polyethylene filler and the unmodified polyethylene fixed biomass shows that the modified fixed biomass can be improved by 18%, and the film forming amount is obviously increased.
3) The prepared modified filler is used in a MBBR reactor, the Hydraulic Retention Time (HRT) is set to be 4 hours, the concentration of COD and ammonia nitrogen in sewage is respectively reduced from 397.4 mg/L and 48.6mg/L to 23.5 mg/L and 4.3mg/L, and the removal rates of COD and ammonia nitrogen are respectively 94.08% and 91.2%.
Under the same conditions, the removal rates of COD and ammonia nitrogen of the unmodified polyethylene filler are 85.08% and 80.32%, respectively. The modified polyethylene filler can obviously improve the removal rate of COD and ammonia nitrogen.
Example 2
The embodiment provides a modification method of polyethylene suspension filler for MBBR (moving bed biofilm reactor), which specifically comprises the following steps:
s1, soaking a cake-shaped polyethylene filler (25 multiplied by 10 mm) in an acidic potassium dichromate solution at 60 ℃ for 2 hours, wherein the acidic potassium dichromate solution is a mixed solution of sulfuric acid and potassium dichromate, the concentration of the potassium dichromate in the mixed solution is 6mol/L, the concentration of the sulfuric acid is 3mol/L, and then taking out the polyethylene filler, washing off a brown layer on the surface by water, and draining;
s2, placing the drained polyethylene filler into a 0.01mol/L phosphoric acid buffer solution, soaking for 2.5 hours, taking out the solution after the solution is neutral, and naturally airing;
s3, mixing a silane coupling agent KH-570, ethanol and water according to a mass ratio of 20:72:8 to prepare a coupling agent hydrolysis solution, wherein the pH value is 6.0, and hydrolyzing for 15min for later use; soaking the dried polyethylene filler in a coupling agent hydrolysis solution at 40 ℃ for stirring for 12 hours, taking out the filler, draining, adding the filler into a mixed solution of powdered activated carbon (the concentration in the mixed solution is 8 g/L) and gelatin protein (the concentration in the mixed solution is 2 g/L), heating to 37 ℃ and stirring for 18 hours;
s4, taking out the filler, flushing with water, and naturally airing to obtain the modified filler for sewage treatment.
The unmodified filler was used as a control and the modified filler was tested separately as follows:
1) Through testing, the surface potential of the polyethylene filler is changed from-20 mV before modification to 1168mV after modification.
2) And placing the filler in a reactor for film forming experiments, wherein after modification, the filler 11d is marked by artemia, clockworm and the like to finish film forming, and the unmodified filler needs 14d to finish film forming.
Analysis of the modified polyethylene filler and the unmodified polyethylene fixed biomass shows that the modified fixed biomass can be improved by 22%, and the film forming amount is obviously increased.
3) The prepared modified filler is used in a MBBR reactor, the HRT is set to be 6 hours, the concentration of COD and ammonia nitrogen in sewage is respectively reduced from 600 mg/L and 65.4mg/L to 45.12 mg/L and 6.3mg/L, and the removal rates of COD and ammonia nitrogen are respectively 92.48% and 90.4%.
Under the same conditions, the removal rates of COD and ammonia nitrogen of the unmodified polyethylene filler are 88.65% and 82.38%, respectively. The modified polyethylene filler can obviously improve the removal rate of COD and ammonia nitrogen.
Example 3
The embodiment provides a modification method of polyethylene suspension filler for MBBR (moving bed biofilm reactor), which specifically comprises the following steps:
s1, soaking a cake-shaped polyethylene filler (25 multiplied by 10 mm) in an acidic potassium dichromate solution at 50 ℃ for 4 hours, wherein the acidic potassium dichromate solution is a mixed solution of sulfuric acid and potassium dichromate, the concentration of the potassium dichromate in the mixed solution is 8mol/L, and the concentration of the sulfuric acid is 3mol/L, then taking out the polyethylene filler, washing off a brown layer on the surface by water, and draining;
s2, placing the drained filler into a 0.01mol/L phosphoric acid buffer solution for soaking for 3 hours, taking out the solution after the solution is neutral, and naturally airing;
s3, mixing a silane coupling agent CS-311, ethanol and water according to a mass ratio of 20:72:8 to prepare a coupling agent hydrolysis solution, wherein the pH value is 6.0, and hydrolyzing for 15 minutes for later use; soaking the dried polyethylene filler in a coupling agent hydrolysis solution at 40 ℃ for stirring for 12 hours, taking out the filler, draining, adding the filler into a mixed solution of powdered activated carbon (the concentration in the mixed solution is 24 g/L) and gelatin protein (the concentration in the mixed solution is 2 g/L), heating to 37 ℃ and stirring for 24 hours;
s4, taking out the filler, flushing with water, and naturally airing to obtain the modified filler for sewage treatment.
The unmodified filler was used as a control and the modified filler was tested separately as follows:
1) Through testing, the surface potential of the polyethylene filler is changed from-20 mV before modification to 200mV after modification.
2) And placing the filler in a reactor for film forming experiments, wherein after modification, the filler 10d is marked by artemia, clockworm and the like to finish film forming, and the unmodified filler needs 14d to finish film forming.
Analysis of the modified polyethylene filler and the unmodified polyethylene fixed biomass shows that the modified fixed biomass can be improved by 20%, and the film forming amount is obviously increased.
4) The prepared modified filler is used in a MBBR reactor, the HRT is set to be 4 hours, the concentration of COD and ammonia nitrogen in sewage is respectively reduced from 226 mg/L and 25.44mg/L to 11.11 mg/L and 0.88mg/L, and the removal rates of COD and ammonia nitrogen are respectively 95.08% and 96.55%.
Under the same conditions, the removal rates of COD and ammonia nitrogen of the unmodified polyethylene filler are 83.2% and 84.32%, respectively. The modified polyethylene filler can obviously improve the removal rate of COD and ammonia nitrogen.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (7)
1. A method for modifying a polyethylene suspension filler for a moving bed biofilm reactor, comprising the steps of:
s1, soaking polyethylene filler in an acidic potassium dichromate solution for 2-4 hours at the temperature of 40-60 ℃, taking out, washing off a brown layer on the surface by water, and draining;
s2, placing the drained polyethylene filler into a phosphoric acid buffer solution for soaking for a period of time, taking out, washing with water, and naturally airing after the leacheate is neutral;
s3, soaking the dried polyethylene filler in a coupling agent hydrolysis solution at the temperature of 25-40 ℃ and stirring for 6-12h, taking out the filler and draining, adding the filler into a mixed solution of powdered activated carbon and gelatin protein, heating to the temperature of 25-40 ℃ and stirring for 18-36h;
s4, taking out the filler, flushing with water, and naturally airing to obtain the polyethylene suspension filler for the moving bed biomembrane reactor.
2. The method for modifying a polyethylene suspension filler for a moving bed biofilm reactor of claim 1, wherein the acidic potassium dichromate mixed solution is a mixed solution of sulfuric acid and potassium dichromate.
3. The method for modifying a polyethylene suspension filler for a moving bed biofilm reactor according to claim 2, wherein the concentration of potassium dichromate contained in the acidic potassium dichromate mixed solution is 6 to 8mol/L and the concentration of sulfuric acid contained therein is 2 to 4mol/L.
4. The method for modifying a polyethylene suspended filler for a moving bed biofilm reactor according to claim 1, wherein the coupling agent in the aqueous solution of the coupling agent is one or a combination of more than two of a silane coupling agent KH-560, a silane coupling agent KH-570 and a titanate coupling agent CS-311.
5. The method for modifying a polyethylene suspension filler for a moving bed biofilm reactor according to claim 1 or 4, wherein the method for preparing the coupling agent hydrolysis solution is as follows: mixing coupling agent, ethanol and water according to the mass ratio of 20:72:8, regulating pH to 5.5-6.5, hydrolyzing for 10-20min for later use.
6. The method for modifying a polyethylene suspension filler for a moving bed biofilm reactor according to claim 1, wherein the concentration of phosphoric acid in the phosphoric acid buffer solution in the step S2 is 0.01-0.02mol/L, and the soaking time of the polyethylene filler therein is 2-3h.
7. The method for modifying a polyethylene suspension filler for a moving bed biofilm reactor according to claim 1, wherein the mixed solution of powdered activated carbon and gelatin protein in step S3 contains 16-32g/L activated carbon and 2-4g/L gelatin protein.
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