CN115231692A - Synchronous nitrogen and phosphorus removal filler and preparation method thereof - Google Patents
Synchronous nitrogen and phosphorus removal filler and preparation method thereof Download PDFInfo
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- CN115231692A CN115231692A CN202211166540.8A CN202211166540A CN115231692A CN 115231692 A CN115231692 A CN 115231692A CN 202211166540 A CN202211166540 A CN 202211166540A CN 115231692 A CN115231692 A CN 115231692A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 40
- 239000011574 phosphorus Substances 0.000 title claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 239000000945 filler Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 10
- 230000001360 synchronised effect Effects 0.000 title description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- 230000001651 autotrophic effect Effects 0.000 claims abstract description 9
- 241000894006 Bacteria Species 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- -1 hydrogen ions Chemical class 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 229910021646 siderite Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 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 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F3/10—Packings; Fillings; Grids
- C02F3/104—Granular carriers
-
- 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
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- 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
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The filler comprises a phosphorus adsorption material component A, a component B serving as an electron donor of sulfur autotrophic denitrifying bacteria and a component C for adjusting the pH value; the three components are calculated according to the mass portion: 1-2 parts of component A, 6-8 parts of component B and 1-2 parts of component C. The invention has high-efficiency phosphorus adsorption effect, and no redundant sludge is generated in the adsorption process; certain hydroxyl radicals can be released in the phosphorus adsorption process, and hydrogen ions released in the sulfur autotrophic denitrification process can be neutralized, so that the purpose of stabilizing the pH value of effluent is achieved; the material has developed pores to form low-density filler, which is beneficial to the nitrogen and phosphorus removal reaction.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a filler for synchronously removing nitrogen and phosphorus and a preparation method of the filler.
Background
With the increasing importance of society on surface water environment, the problem of excessive propagation of algae caused by excessive concentration of nitrogen and phosphorus in water is also increasingly emphasized. The key for improving the quality of the water ecological environment in the current and the next 10 years is to realize the high-efficiency reduction and limit control of the concentration of nitrogen and phosphorus in water and eliminate the eutrophication of a water body.
At present, the water quality indexes of most domestic urban sewage treatment plants cannot meet the requirement of resource recycling, and deep removal of items such as total phosphorus, total nitrogen and the like in water is required. The invention patent of China 'a siderite-based nitrogen and phosphorus removal material and a using method thereof (ZL 201410063868.6)', discloses a technical scheme that ferrous iron in siderite is used as an electron donor to reduce nitrate into nitrogen under the action of nitrate iron oxidizing bacteria, and ferrous ions are oxidized into ferric ions. The siderite is taken as a material with microbial activity, so that the advanced treatment of synchronous nitrogen and phosphorus removal of wastewater can be realized. Wherein iron and ferrous iron particles and phosphate precipitate to remove phosphorus, and siderite plays an important role as a carbon source. The patent teaches the value of siderite in the field of denitrification. However, the siderite has a limited effect in biological denitrification due to low utilization rate, and can only be used for treating micro-polluted wastewater. Therefore, the development and utilization of siderite in the aspect of denitrification treatment are still to be improved.
Another Chinese invention patent ZL201710636570.3 discloses a method for treating sewage by strengthening synchronous nitrogen and phosphorus removal in a sulfur autotrophic denitrification process, which adopts pyrite and sulfur as sulfur sources and siderite as carbon sources. The siderite utilization by the thalli is enhanced by the synergistic effect of the pyrite and the sulfur, so that the denitrification capability is enhanced; the pyrite and siderite release iron and ferrous ions and phosphate ions form iron phosphate precipitates, so that the phosphorus removal capacity is enhanced. However, in the process of removing phosphorus by adopting the method, the generated phosphate precipitation can cause the increase of suspended matters in the system, thereby improving the backwashing frequency and increasing the residual sludge amount. Therefore, the method has certain optimization space for synchronous nitrogen and phosphorus removal.
In conclusion, in the field of sewage treatment, the prior art is difficult to realize the purpose of high-efficiency denitrification and dephosphorization at the same time.
Disclosure of Invention
Aiming at the defects of the existing filler or method mentioned in the background technology, the invention provides the filler which can achieve the purpose of high-efficiency nitrogen and phosphorus removal integration, and provides the preparation method of the filler.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows: a filler for synchronously removing nitrogen and phosphorus comprises a phosphorus adsorption material component A, a component B serving as an electron donor of sulfur autotrophic denitrifying bacteria and a component C for adjusting the pH value;
the three components are calculated according to the mass portion: 1-2 parts of component A, 6-8 parts of component B and 1-2 parts of component C.
The component A is a phosphorus adsorption material mainly comprising beta-iron oxyhydroxide.
The preparation method of the component A comprises the following steps:
s1, preparing an iron salt solution with the concentration of 0.1-0.5 mol/L;
s2, dropwise adding alkali liquor with the concentration of 0.5-1mol/L into the solution obtained in the step S1 until the pH =7-8, and stopping adding the alkali liquor;
s3, adding 10-40% of polyethylene glycol aqueous solution dropwise into the mixed solution obtained in the step S2 until the mass fraction of the polyethylene glycol in the mixed solution reaches 0.5-2%, stopping adding dropwise, and fully mixing;
s4, heating the mixed liquor obtained in the step S3 to 90-100 ℃, quickly stirring, and oxidizing for 15-24 hours by using air;
s5, after the reaction is finished, separating the obtained solid material from the mixed solution, drying and crushing the washed solid material to obtain a powdery material with the particle size of 100-200 meshes, and obtaining the component A.
The ferric salt solution in the step S1 is one or a mixture of ferrous nitrate, ferrous chloride and ferrous sulfate.
The alkali solution in the step S2 is a sodium hydroxide solution, a potassium hydroxide solution or ammonia water.
The component B is sulfur.
The component C is limestone powder.
A process for the preparation of a filler,
SS1 component A, component B and component C are mixed according to the mass ratio of 1-2:6-8:1-2;
SS2, placing the mixture in a reaction kettle, heating to 110-150 ℃, and stirring the mixture uniformly after the sulfur of the component B is completely melted;
SS3, transferring the molten mixture into a closed mold, immediately injecting nitrogen with a certain volume into the mixture, wherein the volume ratio of the nitrogen to the mixture is 1-2;
and (3) crushing the cooled SS4 material to form a biological carrier material with the size of 5-10 mm.
The biological carrier material after the crushing treatment in the step SS4 has a rich pore structure.
Compared with the prior art, the invention has the advantages that through the technical scheme:
1. the filler has high-efficiency phosphorus adsorption effect, and no excess sludge is generated in the adsorption process;
2. certain hydroxyl radicals can be released in the phosphorus adsorption process, and hydrogen ions released in the sulfur autotrophic denitrification process can be neutralized, so that the purpose of stabilizing the pH value of effluent is achieved;
3. the material has developed pores to form low-density filler, which is beneficial to the nitrogen and phosphorus removal reaction.
Drawings
FIG. 1 is a graph of the total nitrogen change of effluent;
FIG. 2 is a graph showing the change of total phosphorus in effluent.
Detailed Description
In order to make the advantages of the material of the present invention clearer, the advantages of the material of the present invention in simultaneous denitrification and dephosphorization are demonstrated by the following specific examples. Those skilled in the art can readily appreciate from the disclosure of the present invention that various modifications and variations can be made in the present invention.
The synchronous nitrogen and phosphorus removal filler comprises a phosphorus adsorption material which mainly comprises beta-iron oxyhydroxide, namely a component A; sulphur as an electron donor for sulphur autotrophic denitrifying bacteria, component B; limestone powder for adjusting the pH value, namely component C. The three components are calculated according to the mass portion: 1-2 parts of component A, 6-8 parts of component B and 1-2 parts of component C.
The preparation method of the component A comprises the following steps:
s1, preparing an iron salt solution with the concentration of 0.1-0.5 mol/L;
s2, dropwise adding alkali liquor with the concentration of 0.5-1mol/L into the solution obtained in the step S1 until the pH =7-8, and stopping adding the alkali liquor;
s3, dropwise adding a 10-40% polyethylene glycol aqueous solution into the mixed solution obtained in the step S2 until the mass fraction of polyethylene glycol in the mixed solution reaches 0.5-2%, stopping dropwise adding, and fully mixing;
s4, heating the mixed liquor obtained in the step S3 to 90-100 ℃, quickly stirring, and oxidizing for 15-24 hours by using air;
s5, after the reaction is finished, separating the obtained solid material from the mixed solution, drying and crushing the washed solid material to obtain a powdery material with the particle size of 100-200 meshes, and obtaining the component A.
As a preferable technical solution, the ferric salt solution in step S1 is one or more of solutions of ferrous nitrate, ferrous chloride and ferrous sulfate.
As a preferable technical solution, the alkali solution in step S2 is one of a sodium hydroxide solution, a potassium hydroxide solution, and ammonia water.
The preparation method of the filler comprises the following steps:
SS1 component A, component B and component C are mixed according to the mass ratio of 1-2:6-8:1-2; a phosphorus adsorbing material taking beta-iron oxyhydroxide as a main component, namely a component A; taking sulfur as an electron donor of sulfur autotrophic denitrifying bacteria, namely a component B; limestone powder for adjusting the pH value, namely a component C;
SS2, placing the mixture in the last step into a reaction kettle, heating to 110-150 ℃, and stirring the mixture uniformly after the sulfur as the component B is completely melted;
SS3, transferring the molten mixture obtained in the last step into a closed mould, immediately injecting nitrogen with a certain volume into the mixture, wherein the volume ratio of the nitrogen to the mixture is 1-2;
and SS4, crushing the material cooled in the previous step to form a biological carrier material with the size of 5-20 mm.
The biological carrier material has rich pore structure and average grain size of 15mm.
The above-described scheme is further illustrated by the following specific examples.
The filler for synchronous denitrification and dephosphorization comprises the following components: a phosphorus adsorption material mainly comprising beta-iron oxyhydroxide, namely a component A; sulfur is used as an electron donor of sulfur autotrophic denitrifying bacteria, namely a component B; limestone powder for adjusting the pH value, namely component C.
In the embodiment, a ferric chloride solution with a concentration of 0.2mol/L is prepared, the ferric chloride solution is dropwise added into 1mol/L of ammonia water, the adding is stopped when the reaction is carried out under the stirring condition until the pH =7.5, polyethylene glycol is added into the mixed solution until the concentration of the polyethylene glycol is 0.5%, the mixed solution is heated to 90 ℃, and the reaction is carried out for 15 hours under the rapid stirring condition. After the reaction is finished, powder with the particle size of 150 meshes is obtained through solid-liquid separation, drying and crushing, namely the component A.
Mixing the components A15 parts, sulfur 70 parts and limestone powder 15 parts by weight, heating the mixture in a reaction kettle to 145 ℃, stirring until the sulfur is completely molten, transferring the uniformly mixed material into a closed mold, introducing nitrogen according to the volume ratio of the nitrogen to the molten mixture of 1.
The following description will be made with reference to comparative data.
The materials are filled into an up-flow bioreactor, and activated sludge is added into the reaction period at the same time, so that the concentration of the activated sludge in the reaction period is ensured to be 2000-4000mg/L. The reactor inlet water is simulated waste water prepared by tap water, and the main water quality indexes are as follows: nitrate nitrogen 50mg/L, bicarbonate alkalinity (calculated as calcium carbonate) 350mg/L, total phosphorus 15mg/L, sulfate 100mg/L. The retention time of the simulated wastewater in the reactor is 7h, the reaction temperature is 27 +/-2 ℃, and the concentration of dissolved oxygen in the reactor is controlled to be less than 0.2mg/L.
In contrast, a control filler was prepared using component C instead of component A, and the control experiment was performed without changing other conditions.
The concentration changes of the total nitrogen and the total phosphorus of the effluent in the reaction process are measured and shown in figures 1 and 2;
as is clear from FIG. 1, the denitrification effect was substantially the same between the working group and the control group, and the addition of component A did not affect the denitrification effect. As can be seen from FIG. 2, under the same conditions, the concentration of total phosphorus in the effluent of the working group is significantly lower than that of the control group, i.e., the filler of the working group has a good effect of removing the total phosphorus in the water.
Claims (8)
1. The filler for simultaneous denitrification and dephosphorization is characterized in that: comprises a phosphorus adsorption material component A, a component B used as an electron donor of sulfur autotrophic denitrifying bacteria and a component C used for adjusting the pH value; the component A is a phosphorus adsorption material mainly comprising beta-iron oxyhydroxide;
the three components are calculated according to the mass portion: 1-2 parts of component A, 6-8 parts of component B and 1-2 parts of component C.
2. The filler for simultaneous phosphorus and nitrogen removal according to claim 1, wherein: the preparation method of the component A comprises the following steps:
s1, preparing an iron salt solution with the concentration of 0.1-0.5 mol/L;
s2, dropwise adding alkali liquor with the concentration of 0.5-1mol/L into the solution obtained in the step S1 until the pH =7-8, and stopping adding the alkali liquor;
s3, adding 10-40% of polyethylene glycol aqueous solution dropwise into the mixed solution obtained in the step S2 until the mass fraction of the polyethylene glycol in the mixed solution reaches 0.5-2%, stopping adding dropwise, and fully mixing;
s4, heating the mixed liquor obtained in the step S3 to 90-100 ℃, quickly stirring, and oxidizing for 15-24h by using air;
s5, after the reaction is finished, separating the obtained solid material from the mixed solution, drying and crushing the washed solid material to obtain a powdery material with the particle size of 100-200 meshes, and obtaining the component A.
3. The filler for simultaneous phosphorus and nitrogen removal according to claim 2, wherein: the ferric salt solution in the step S1 is one or a mixture of ferrous nitrate, ferrous chloride and ferrous sulfate.
4. The filler for simultaneous phosphorus and nitrogen removal according to claim 2, wherein: the alkali solution in the step S2 is a sodium hydroxide solution, a potassium hydroxide solution or ammonia water.
5. The filler for simultaneous phosphorus and nitrogen removal according to claim 1, wherein: the component B is sulfur.
6. The filler for simultaneous phosphorus and nitrogen removal according to claim 1, wherein: the component C is limestone powder.
7. A process for the preparation of the filler according to any one of claims 1 to 6, characterized in that:
SS1 component A, component B and component C are mixed according to the mass ratio of 1-2:6-8:1-2;
SS2, placing the mixture in a reaction kettle, heating to 110-150 ℃, and stirring the mixture uniformly after the sulfur of the component B is completely melted;
SS3, transferring the molten mixture into a closed mold, immediately injecting nitrogen with a certain volume into the mixture, wherein the volume ratio of the nitrogen to the mixture is 1-2;
and (3) crushing the cooled SS4 material to form a biological carrier material with the size of 5-10 mm.
8. The method of claim 7, wherein: the biological carrier material after the crushing treatment in the step SS4 has a rich pore structure.
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