CN117720198B - Composite modified MBBR (moving bed biofilm reactor) filler and preparation method and application thereof - Google Patents
Composite modified MBBR (moving bed biofilm reactor) filler and preparation method and application thereof Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 60
- -1 amino modified activated carbon Chemical class 0.000 claims abstract description 38
- 239000006247 magnetic powder Substances 0.000 claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 7
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 7
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical class BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 claims abstract 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 239000010865 sewage Substances 0.000 claims description 17
- 238000005520 cutting process Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000035939 shock Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 239000010802 sludge Substances 0.000 abstract description 13
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 16
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- 244000005700 microbiome Species 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009881 electrostatic interaction Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009474 hot melt extrusion Methods 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a composite modified MBBR filler, a preparation method and application thereof, wherein the composite modified MBBR filler comprises the following components in parts by mass: 80-180 parts of HDPE, 1-8 parts of ferroferric oxide magnetic powder, 1-8 parts of PAM powder, 1-6 parts of amino modified activated carbon powder, 1-5 parts of carboxyl modified zeolite powder, 1-5 parts of calcium carbonate powder, 1-3 parts of silicone powder and 1-3 parts of paraffin oil. The electronegativity of the composite modified MBBR filler is weakened, the specific surface area is large, and simultaneously, activated sludge and pollutants can be adsorbed on the surface of the filler by utilizing the adsorption effect of amino modified activated carbon powder, so that the film forming time is shortened, ferroferric oxide magnetic powder is highly dispersed in a system, and the treatment efficiency is cooperatively improved.
Description
Technical Field
The invention relates to a composite modified MBBR filler, and a preparation method and application thereof, and belongs to the technical field of sewage treatment.
Background
The MBBR technology principle is to increase biomass and biological species in the reactor by adding a certain amount of suspension carriers into the reactor, thereby increasing the treatment efficiency of the reactor. In the MBBR process, microorganisms are attached and grown on the surface of the suspension carrier in a form of a biological film, so that the influence of hydraulic retention time is avoided, and a better living environment is provided for microorganisms with longer sludge age. Meanwhile, the diversity and the richness of microorganisms in the reactor are improved. Therefore, compared with an activated sludge process, the MBBR has better sewage treatment effect.
MBBR filler is the core of MBBR process and is the place for enriching microorganisms. The MBBR filler is a biological carrier which is formed by taking polyethylene, polypropylene, polyurethane and other plastics as raw materials and processing and shaping the raw materials through an extrusion molding/injection molding process. Compared with a foam carrier prepared from polyurethane, a carrier prepared from polyolefin such as polyethylene, polypropylene and the like has the advantages of low cost, high yield, good fluidization effect, high mechanical strength and good mass transfer effect, and is widely popularized and applied in actual sewage treatment. However, due to the limitations (such as hydrophobicity and negative charge) of high polymer materials such as polyethylene, polypropylene and the like, the preparation is poor, the film forming speed is slow, and the film forming amount is small, so that the starting period and the processing performance of the MBBR process are affected, and the application of the MBBR process in practical engineering is restricted. It is therefore necessary to modify the material itself accordingly for its inherent drawbacks.
Disclosure of Invention
The invention aims to provide a composite modified MBBR filler, a preparation method and application thereof, wherein electronegativity of the composite modified MBBR filler is weakened, specific surface area is large, activated sludge and pollutants can be adsorbed on the surface of the filler by utilizing adsorption of amino modified activated carbon powder, film forming time is shortened, ferroferric oxide magnetic powder is highly dispersed in a system, and treatment efficiency is cooperatively improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the composite modified MBBR filler comprises the following components in parts by weight: 80-180 parts of HDPE, 1-8 parts of ferroferric oxide magnetic powder, 1-8 parts of PAM powder, 1-6 parts of amino modified activated carbon powder, 1-5 parts of carboxyl modified zeolite powder, 1-5 parts of calcium carbonate powder, 1-3 parts of silicone powder and 1-3 parts of paraffin oil.
Preferably, the preparation method of the amino modified activated carbon comprises the following steps: mixing active carbon and ammonia water, stirring and heating to obtain suspension; and (3) centrifugally dehydrating the suspension, and drying to obtain the amino modified activated carbon.
Preferably, the ratio of the activated carbon to the ammonia water is 1g: (5-30) ml, and the concentration of ammonia water is not less than 1%;
the heating conditions are as follows: 50-80 ℃ for 1-10h;
the drying conditions are as follows: 40-60 ℃ for 2-7h.
Preferably, the preparation method of the carboxyl modified zeolite powder comprises the following steps: placing zeolite powder in organic acid, vibrating at constant temperature, standing, removing supernatant, washing to neutrality, and drying to obtain carboxyl modified zeolite powder; wherein the organic acid contains at least two carboxyl groups.
Preferably, the ratio of the zeolite powder to the organic acid is as follows: (1-5) g: (100-200) ml, and the concentration of the organic acid is 0.3-0.5mol/L.
Preferably, the organic acid is any one of oxalic acid, malonic acid, succinic acid and glutaric acid.
Preferably, the conditions of the constant temperature oscillation are as follows: ultrasonic oscillation is carried out for 6-8h at 15-20 ℃ and ultrasonic frequency is 30-50KHz.
The preparation method of any of the composite modified MBBR fillers comprises the following steps:
s1, putting raw materials into a mixer, and stirring to obtain a mixture; carrying out hot melting granulation on the mixture to obtain mixture particles;
S2, hot melting and extruding the mixture particles, cooling, shaping and cutting to obtain the filler;
and S3, soaking the filler obtained by cutting in the step S2 in acid liquor, flushing and drying, and magnetizing to obtain the composite modified MBBR filler.
Preferably, in the step S3, the acid solution is sulfuric acid solution with pH less than or equal to 2, and the soaking time is 1-3h; the magnetizing voltage is 500-1200V.
The application of any of the composite modified MBBR filler in sewage treatment.
The invention has the beneficial effects that:
1. By adding cationic PAM powder into HDPE, the Zeta potential of the filler can be improved, the electronegativity of the filler is weakened, and the filler can absorb sludge in water better;
2. Calcium carbonate powder is added into the MBBR filler, and sulfuric acid is used for soaking the formed filler to corrode the surface calcium carbonate, so that the specific surface area of the MBBR filler can be increased; meanwhile, the amino modified activated carbon powder has an adsorption effect, so that activated sludge and pollutants can be adsorbed on the surface of the filler, the treatment efficiency is improved, and the film forming time is shortened;
3. the amino groups on the surface of the amino modified activated carbon powder can perform physical adsorption with the magnetic centers on the surface of the ferroferric oxide magnetic powder, so that the ferroferric oxide magnetic powder is adsorbed on the activated carbon and forms Fe-N tri-coordination ions, and the ions have partial positive charges, so that the Fe-N tri-coordination ions can perform electrostatic interaction with other negatively charged components on the surface of the amino modified activated carbon powder, and the dispersibility of the ferroferric oxide magnetic powder in a system is improved;
the zeolite powder can carry a certain negative charge through carboxyl modification, so that electrostatic interaction can be generated between the zeolite powder and Fe-N tri-coordination ions, and the dispersibility of the ferroferric oxide magnetic powder is further improved; and the carboxyl can also lead the powder to generate repulsive interaction, thereby reducing the occurrence of magnetic powder agglomeration phenomenon and being beneficial to improving the sewage treatment performance of the filler.
Drawings
FIG. 1 is a flow chart of the preparation of a composite modified MBBR filler;
FIG. 2 is a graph showing the COD removing effect of the filler provided in examples 1 to 3 and comparative example 3 on sewage;
FIG. 3 is a graph showing the removal efficiency of COD in sewage by the fillers provided in examples 1 to 3 and comparative example 3;
FIG. 4 is a graph showing the effect of the filler provided in examples 1-3 and comparative example 3 on ammonia nitrogen removal from wastewater;
FIG. 5 is a graph showing the removal efficiency of ammonia nitrogen from wastewater by the filler provided in examples 1-3 and comparative example 3.
Detailed Description
The invention is described in detail below with reference to the drawings and examples.
In the following examples and comparative examples, the mesh number of the powder raw materials used was not less than 200 mesh, and the preparation flow of the composite modified MBBR filler is shown in FIG. 1.
The preparation method of the amino modified activated carbon comprises the following steps: 10g of activated carbon was added to 100mL of 10% aqueous ammonia solution, and the solution was heated to 60℃and reacted with stirring for 8 hours. After the reaction, the activated carbon suspension is centrifuged for 30min at 8000r/min, then the supernatant is removed, then ultrapure water is added for repeated cleaning for 4 times, and then the mixture is placed in an oven and dried for 4 hours at 50 ℃.
The preparation method of the carboxyl modified zeolite powder comprises the following steps: 5g zeolite powder is placed in 150ml succinic acid solution with the concentration of 0.3mol/L, ultrasonic oscillation is carried out for 6 hours at the temperature of 15 ℃ and the frequency of 50KHz, the supernatant is removed after standing, and the carboxyl modified zeolite powder is obtained after washing to be neutral.
The average removal rate referred to herein is the average of the data measured from day 1 to day 30.
Example 1
1. Mixing: 120 parts of HDPE, 2 parts of ferroferric oxide magnetic powder, 1.5 parts of PAM powder, 2.5 parts of amino modified activated carbon powder, 2 parts of carboxyl modified zeolite powder, 3 parts of calcium carbonate powder, 1.2 parts of silicone powder and 1.3 parts of paraffin oil are taken, and are put into a mixer, and a stirring and mixing switch is turned on to mix for 10 minutes.
2. And (5) hot melting granulation: and pouring the mixture into a granulator for hot melting granulation to obtain mixture particles.
3. And (3) shaping and extruding: and pouring the mixture particles into a double-screw extruder for hot melt molding, and setting the temperatures of the 3 hot areas to 160 ℃,170 ℃ and 180 ℃ respectively for hot melt extrusion.
4. And (5) shaping and cooling: and regulating the negative pressure of the vacuum cooler to-0.2 Mpa, and opening tap water and a vacuum pump switch to cool and shape.
5. Cutting a finished product: cutting interval of the cutting machine is set to be 10mm, and the packing is obtained through cutting.
6. Acid soaking corrosion: the filler is placed in sulfuric acid solution with pH value of 1 for soaking for 2 hours, and then is washed clean and dried by tap water.
7. Magnetizing: and (3) placing the aired filler in a magnetizer, and magnetizing the filler by using 800V voltage to obtain the composite modified MBBR filler.
Example 2
1. Mixing: 140 parts of HDPE, 3 parts of ferroferric oxide magnetic powder, 2 parts of PAM powder, 3 parts of amino modified activated carbon powder, 2.5 parts of carboxyl modified zeolite powder, 3.5 parts of calcium carbonate powder, 1.5 parts of silicone powder and 1.6 parts of paraffin oil are taken, and are put into a mixer, and a stirring and mixing switch is turned on to mix for 10 minutes.
2. And (5) hot melting granulation: and pouring the mixture into a granulator for hot melting granulation to obtain mixture particles.
3. And (3) shaping and extruding: and pouring the mixture particles into a double-screw extruder for hot melt molding, and setting the temperatures of the 3 hot areas to 160 ℃,170 ℃ and 180 ℃ respectively for hot melt extrusion.
4. And (5) shaping and cooling: and regulating the negative pressure of the vacuum cooler to-0.2 Mpa, and opening tap water and a vacuum pump switch to cool and shape.
5. Cutting a finished product: cutting interval of the cutting machine is set to be 10mm, and the packing is obtained through cutting.
6. Acid soaking corrosion: the filler is placed in sulfuric acid solution with pH value of 1 for soaking for 2 hours, and then is washed clean and dried by tap water.
7. Magnetizing: and (3) placing the aired filler in a magnetizer, and magnetizing the filler by using 800V voltage to obtain the composite modified MBBR filler.
Example 3
1. Mixing: 160 parts of HDPE, 3.2 parts of ferroferric oxide magnetic powder, 2.3 parts of PAM powder, 3.2 parts of modified activated carbon powder, 2.8 parts of carboxyl modified zeolite powder, 3.8 parts of calcium carbonate powder, 1.8 parts of silicone powder and 1.9 parts of paraffin oil are taken, and are put into a mixer, and a stirring and mixing switch is turned on to mix for 10 minutes.
2. And (5) hot melting granulation: and pouring the mixture into a granulator for hot melting granulation to obtain mixture particles.
3. And (3) shaping and extruding: and pouring the mixture particles into a double-screw extruder for hot melt molding, and setting the temperatures of the 3 hot areas to 160 ℃,170 ℃ and 180 ℃ respectively for hot melt extrusion.
4. And (5) shaping and cooling: and regulating the negative pressure of the vacuum cooler to-0.2 Mpa, and opening tap water and a vacuum pump switch to cool and shape.
5. Cutting a finished product: cutting interval of the cutting machine is set to be 10mm, and the packing is obtained through cutting.
6. Acid soaking corrosion: the filler is placed in sulfuric acid solution with pH value of 1 for soaking for 2 hours, and then is washed clean and dried by tap water.
7. Magnetizing: and (3) placing the aired filler in a magnetizer, and magnetizing the filler by using 800V voltage to obtain the composite modified MBBR filler.
Comparative example 1
Substantially the same as in example 2, except that zeolite powder which was not subjected to carboxyl modification was used in the raw material.
Comparative example 2
Substantially the same as in example 2, except that the activated carbon powder not subjected to amino modification and the zeolite powder not subjected to carboxyl modification were used in the raw materials.
Comparative example 3
The filler is a commercially available K3 filler.
The contact angle, zeta potential, specific surface area and density of the fillers of examples 1 to 3 and comparative example 3 were measured, and the results are shown in Table 1.
TABLE 1 Filler parameters for examples 1-3 and comparative example 3
As can be seen from Table 1, the composite modified MBBR filler obtained in examples 1-3 has a contact angle smaller than that of the commercially available filler, and has good wettability and water compatibility on the surface; the Zeta potential and specific surface area of the composite modified MBBR filler obtained in the embodiment 1-3 are larger than those of the filler sold in the market, the electronegativity is reduced, the specific surface area is increased, the filler can absorb sludge better, and the adhesion quantity of the sludge can be improved.
6 Groups of same MBBR reactors are operated in parallel, wherein the reactors 1-3 are respectively added with the composite modified MBBR filler obtained in the examples 1-3, the reactors 4-5 are respectively added with the MBBR filler obtained in the comparative examples 1-2, the reactor 6 is added with the commercial K3 filler, the filling rate is 30 percent, the reactor is made of organic glass round tubes with the diameter of 190mm and the height of 350mm, the overflow port is 285mm, the effective volume is 8L, an aeration disc is arranged at the bottom of the reactor, an aeration pump is connected, a rotameter is connected in the middle, the aeration amount can be adjusted, and the water inlet pump is a peristaltic pump, and the water inlet flow can be adjusted.
The operation conditions of the 6 groups of reactors are completely the same, the continuous flow water inlet and outlet are realized, the water inlet flow is kept at 1.5L/h during the operation period, and the aeration rate is kept at 0.3L/min. The membrane hanging mode adopts an inoculation sludge discharge method, namely inoculation sludge and filler are firstly subjected to stuffy aeration for 24 hours in a reactor, microorganisms are fully contacted with the filler, and then the sludge is emptied and continuously fed into sewage. Wherein, sewage adopts the raw water of intaking of sewage plant in certain industrial park, monitors each pollutant water outlet index in the period, and when the concentration of the pollutant in the water outlet is stable, the completion of film hanging is indicated.
The pollutant removal index mainly examines 2 indexes of COD and ammonia nitrogen because of the aerobic process adopted by the small test, and the specific removal effect is shown in figures 2-5 and tables 2-3.
TABLE 2 removal of contaminants by the fillers of examples 2 and comparative examples 1-2 (average 5 days after stabilization, unit: mg/L)
Table 3 the removal of contaminants by the fillers of example 2 and comparative examples 1-2 (average 5 days after stabilization, unit:%)
Analysis and comparison of the COD removal effect (figure 2) and the removal rate (figure 3) of the composite modified MBBR filler and the commercial K3 filler show that the effluent index tends to be stable after the 25 th day, wherein the commercial K3 filler has the worst COD removal effect, the average removal rate is 72.23%, the best COD removal effect of the embodiment 2 is the average removal rate is 80.92%.
Analysis and comparison of ammonia nitrogen removal effect (figure 4) and removal rate (figure 5) of the composite modified MBBR filler and the commercial K3 filler show that the effluent index tends to be stable after 25 days, wherein the commercial K3 filler has the worst ammonia nitrogen removal effect, the average removal rate is 59.65%, the best ammonia nitrogen removal effect in example 2 and the average removal rate is 72.79%. Of these, example 2 stabilized fastest and the commercial K3 filler stabilized slowest.
The reason for the phenomenon is that the addition of the cationic PAM powder improves the integral Zeta potential of the filler, so that electronegativity of the filler is weakened, and the filler can better adsorb sludge in water; and the specific surface area of the MBBR filler is increased, and the adsorption effect of the amino modified activated carbon powder can adsorb more activated sludge and pollutants on the surface of the filler, so that the treatment efficiency is improved, and the film forming time is shortened. The amino modified activated carbon can adsorb ammonia nitrogen, nitrate nitrogen and organic matters in sewage in a large amount, provides sufficient nitrogen sources and carbon sources for the proliferation of functional microorganisms, and accelerates the speed and efficiency of purifying the sewage by the microorganisms.
As can be seen from tables 2 to 3, the composite modified MBBR filler provided in example 2 had better removal effect and removal rate of COD and ammonia nitrogen than the MBBR filler provided in comparative examples 1 to 2, and the MBBR filler provided in comparative example 1 had better removal effect and removal rate of COD and ammonia nitrogen than the MBBR filler provided in comparative example 2. The reason is that by modifying the active carbon by amino, the functional group on the surface of the active carbon is changed, the content of the amino is improved, the negative charge on the surface of the active carbon is weakened, and the adhesion of microorganisms on the surface of the active carbon can be accelerated by the electrostatic action. In addition, the amino modified activated carbon can adsorb ammonia nitrogen, nitrate nitrogen and organic matters in the sewage in a large amount, provides sufficient nitrogen sources and carbon sources for the proliferation of functional microorganisms, and accelerates the speed and efficiency of purifying the sewage by the microorganisms. Secondly, the amino groups on the surface of the amino modified activated carbon can perform physical adsorption action with the magnetic centers on the surface of the ferroferric oxide magnetic powder, so that the ferroferric oxide magnetic powder is adsorbed on the activated carbon and forms Fe-N three-coordination ions, the ions have partial positive charges, the Fe-N three-coordination ions can perform electrostatic interaction with other negatively charged components on the surface of the amino modified activated carbon, the dispersibility of the ferroferric oxide magnetic powder in a system is improved, the dispersing effect of the ferroferric oxide magnetic powder is good, the occurrence of agglomeration phenomenon can be reduced, and pollutants in sewage can be removed more comprehensively through adsorption and sedimentation. After the zeolite powder is modified by carboxyl, the zeolite powder can have a certain negative charge, so that electrostatic interaction can be generated between the zeolite powder and Fe-N tri-coordination ions, and the dispersibility of the ferroferric oxide magnetic powder is further improved; and the carboxyl can also lead the powder to generate repulsive interaction, thereby reducing the occurrence of magnetic powder agglomeration phenomenon, and being more beneficial to improving the sewage treatment performance of the filler.
The foregoing is merely illustrative of the preferred embodiments of this invention, and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of this invention, and such variations and modifications are to be regarded as being within the scope of this invention.
Claims (10)
1. The composite modified MBBR filler is characterized by comprising the following components in parts by weight: 80-180 parts of HDPE, 1-8 parts of ferroferric oxide magnetic powder, 1-8 parts of PAM powder, 1-6 parts of amino modified activated carbon powder, 1-5 parts of carboxyl modified zeolite powder, 1-5 parts of calcium carbonate powder, 1-3 parts of silicone powder and 1-3 parts of paraffin oil.
2. The composite modified MBBR filler of claim 1, wherein the amino modified activated carbon is prepared by the steps of: mixing active carbon and ammonia water, stirring and heating to obtain suspension; and (3) centrifugally dehydrating the suspension, and drying to obtain the amino modified activated carbon.
3. The composite modified MBBR filler of claim 2, wherein the ratio of activated carbon to ammonia is 1g: (5-30) ml, and the concentration of ammonia water is not less than 1%;
the heating conditions are as follows: 50-80 ℃ for 1-10h;
the drying conditions are as follows: 40-60 ℃ for 2-7h.
4. The composite modified MBBR filler of claim 1, wherein said carboxy modified zeolite powder is prepared by the steps of: placing zeolite powder in organic acid, vibrating at constant temperature, standing, removing supernatant, washing to neutrality, and drying to obtain carboxyl modified zeolite powder; wherein the organic acid contains at least two carboxyl groups.
5. The composite modified MBBR filler of claim 4, wherein the zeolite powder to organic acid ratio is: (1-5) g: (100-200) ml, and the concentration of the organic acid is 0.3-0.5mol/L.
6. The composite modified MBBR filler of claim 4, wherein said organic acid is any one of oxalic acid, malonic acid, succinic acid and glutaric acid.
7. The composite modified MBBR filler of claim 4, wherein said constant temperature shock conditions are: ultrasonic oscillation is carried out for 6-8h at 15-20 ℃ and ultrasonic frequency is 30-50KHz.
8. The method for preparing the composite modified MBBR filler according to any one of claims 1-7, comprising the steps of:
s1, putting raw materials into a mixer, and stirring to obtain a mixture; carrying out hot melting granulation on the mixture to obtain mixture particles;
s2, hot melting and extruding the mixture particles, cooling and shaping, and cutting to obtain a filler;
and S3, soaking the filler obtained by cutting in the step S2 in acid liquor, flushing and drying, and magnetizing to obtain the composite modified MBBR filler.
9. The preparation method of the composite modified MBBR filler according to claim 8, wherein in the step S3, the acid solution is sulfuric acid solution with pH less than or equal to 2, and the soaking time is 1-3h; the magnetizing voltage is 500-1200V.
10. Use of the composite modified MBBR filler of any of claims 1-7 in sewage treatment.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522972A (en) * | 2003-09-03 | 2004-08-25 | 华南理工大学 | Method for preparing magnetic filling with biological affinity, hydrophilicity and activity for water treatment |
| CN107139497A (en) * | 2017-06-01 | 2017-09-08 | 环能科技股份有限公司 | A kind of preparation method of magnetic water treatment filler |
| CN116715349A (en) * | 2023-06-30 | 2023-09-08 | 南京高科环境科技有限公司 | Preparation method of modified activated carbon, preparation method of microorganism-loaded material and application of microorganism-loaded material |
| CN219947191U (en) * | 2023-04-25 | 2023-11-03 | 南京高科环境科技有限公司 | Modified MBBR packs production extruder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522972A (en) * | 2003-09-03 | 2004-08-25 | 华南理工大学 | Method for preparing magnetic filling with biological affinity, hydrophilicity and activity for water treatment |
| CN107139497A (en) * | 2017-06-01 | 2017-09-08 | 环能科技股份有限公司 | A kind of preparation method of magnetic water treatment filler |
| CN219947191U (en) * | 2023-04-25 | 2023-11-03 | 南京高科环境科技有限公司 | Modified MBBR packs production extruder |
| CN116715349A (en) * | 2023-06-30 | 2023-09-08 | 南京高科环境科技有限公司 | Preparation method of modified activated carbon, preparation method of microorganism-loaded material and application of microorganism-loaded material |
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