CN105836881B - A method of based on low C/N than recycled water advanced nitrogen dephosphorization - Google Patents
A method of based on low C/N than recycled water advanced nitrogen dephosphorization Download PDFInfo
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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
- C02F3/28—Anaerobic digestion processes
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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
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Abstract
It is a kind of based on low C/N than the method for recycled water advanced nitrogen dephosphorization belong to field of environment engineering technology.With alkali process corncob coupling sulphur solid phase cellulose carbon source sulphur iron process, abbreviation SCSC S Fe techniques are formed with sponge Iron-complex-filling.Based on heterotrophic denitrification denitrification, the denitrification of collaboration sulphur autotrophic denitrification and sponge iron jointly removes nitrogen in water SCSC S Fe process systems.System mainly occurs chemical action with sulphur and sponge iron and generates FeS, other products Fe generated in conjunction with sponge iron rot2+、Fe3+、Fe6(OH)12(CO3) and substances such as FeOOH, by adsorption precipitation effect by PO4 3‑It is converted to Fe3(PO4)2·χH2O、FePO4And Fe3(PO4)2(OH)2Precipitation, thus by phosphorus ligands.SCSC S Fe techniques effectively improve low C/N than recycled water advanced nitrogen phosphor-removing effect.The present invention has good application prospect for high-quality recycled water processing.
Description
Technical field
The present invention is originally related to one kind and being suitable for low C/N than recycled water advanced nitrogen phosphorus removing method, is based on solid phase cellulose carbon
The method that source corncob coupling sulphur Iron-complex-filling strengthens advanced nitrogen dephosphorization, belongs to field of environment engineering technology.
Background technology
City water resource crisis annoyings city harmonious development, and reclaimed water reuse is the inevitable way for solving water resources crisis
Diameter.It is limited, is still contained in the water outlet of traditional biological denitrification phosphorous removal technique certain dense by the treatment technology of existing sewage treatment plant
Nitrogen, the phosphorus of degree.Some researches show that nitrogen, phosphorus are the control selectors of most of body eutrophications.For envelopes such as lake, reservoirs
Closing property waters, when inorganic states total nitrogen content is more than 0.2mg.L in water body-1, total phosphorus is more than 0.01mg.L-1When, it is possible to cause
Wawter bloom phenomenon.The quality of the excessively high safety and recycled water for seriously affecting ecology of the content of nitrogen and phosphorous.Therefore, nitrogen, phosphorus in recycled water are controlled
Content is particularly important for ensureing ecological safety and improving recycled water quality.
As municipal sewage plant's tail water at recycled water water source, that there are phosphorus content is low, denitrogenation synchronizes dephosphorization difficulty etc. and asks
Topic.Studies have found that 80% or more nitrogen is existed in the form of nitrate nitrogen in tail water.Cellulose solid-phase carbon source derives from a wealth of sources,
Denitrification effect is good, has unique advantage especially in terms of low C/N is than underground water, tail water denitrification denitrogenation.Common agricultural is beautiful
Meter Xin not only contain abundant cellulose, but also it is cheap, be convenient for attached growth of microorganisms.Some researches show that sodium hydroxides
Treated corncob release carbon source is more longlasting, using more fully.But corncob inner carbon content is limited, can not ensure to continue height
Effect ground denitrification denitrogenation effect, while being difficult to realize denitrification denitrogenation and synchronizing phosphorus ligands.
Sulphur autotrophic denitrification process is that microorganism utilizes inorganic carbon source (such as CO3 2-、HCO3 -), using reduced sulfur as nitrate
The electron donor of reduction carries out, this process without consuming carbon source, be widely used in low C/N than underground water and sewage it is de-
During nitrogen.Sulphur participates in denitrification process as the electron donor of sulphur autotrophic denitrification, the H generated during this+Contribute to
The ph balancing of maintenance system.Meng Chengcheng etc. organically combines the denitrogenation of sulphur autotrophic denitrification and three-diemsnional electrode biomembrane process,
The process of heterotrophic denitrification and sulphur autotrophic denitrification synchronous progress over time and space is realized, and achieves good reinforcing
The pH buffer capacities of denitrification effect and stabilization.Therefore, it is de- to be conducive to make up heterotrophic denitrification using sulphur as reactor filler
The deficiency and systems stabilisation pH value of electron donor during nitrogen.
Sponge iron structural porous is loose, specific surface energy is big, convenient for reacting with water oxygen state substance.In addition, zeroth order
Iron constitutes micro- primary battery with carbon particle and sponge iron is promoted constantly to corrode.The Fe that sponge iron rot generates2+With further oxidation life
At Fe3+And their hyrate Fe (OH)3To PO4 3-Sweep, flocculate with stronger volume, precipitation, by the phosphorus in water with
FePO4It is removed with multinuclear di iron precipitation form.Studies have found that the electronics that sponge iron rot generates may participate in denitrification
Process restores the nitrate nitrogen in water.Therefore, using sponge iron as denitrification filter pool filler, dephosphorization simultaneous denitrification may be implemented
Purpose.
Solid phase cellulose carbon source corncob after alkali process is organically combined to form solid phase cellulose with sulphur Iron-complex-filling
Carbon source sulphur iron process (Solid Carbon Source of Cellulose and sulfur/sponge iron
Process), abbreviation SCSC-S-Fe techniques.Three kinds of denitrifications, respectively heterotrophism are existed simultaneously in SCSC-S-Fe process systems
The denitrification of denitrification, sulphur autotrophic denitrification and sponge iron, wherein based on heterotrophic denitrification denitrification, the anti-nitre of sulphur autotrophy
Change supplemented by the denitrification with sponge iron, the denitrification of sponge iron includes electronation effect, the generation of sponge iron rot again
H2And Fe2+It is acted on for the autotrophic denitrification of electron donor.Cellulose is degraded by microorganisms into easily by heterotrophic denitrification in corncob
The organic carbon source that bacterium utilizes promotes the progress of heterotrophic denitrification denitrification process；Heterotrophic denitrification was acted on by carbon source not at that time
When foot limitation, the denitrification of sulphur autotrophic denitrification and sponge iron enhances, to guarantee system maintenance stability and high efficiency denitrogenation effect
Rate.
Meanwhile there is chemistry and the dual dephosphorization function of biology in SCSC-S-Fe systems, wherein being act as with chemical dephosphorization
It is main, supplemented by biological phosphate-eliminating effect.Chemical dephosphorization effect is mainly completed by sponge iron corrosion process.The corrosion of sponge iron because
Element is in addition to dissolved oxygen, micro- primary battery and nitrate nitrogen, and the organic acid combination sulphur generated during cellulose degradation in corncob is certainly
Support the H that denitrification process generates+Collectively promote the corrosion of sponge iron.The Fe that sponge iron rot generates2+、Fe3+And its hydrolysate
It is acted on phosphorus ligands with adsorption precipitation.Therefore, SCSC-S-Fe techniques are for promoting reclaimed water reuse to be of great significance.
Invention content
The present invention propose it is a kind of based on low C/N than recycled water advanced nitrogen dephosphorization method.
Technical scheme of the present invention to achieve the above object, which is characterized in that microorganism is by cellulose in corncob and partly
Cellulose degradation is the organic matter utilized for heterotrophic denitrification bacterium, promotes heterotrophic denitrification denitrification.System is with heterotrophism
Based on denitrification, when carbon source deficiency, the denitrification of sulphur autotrophic denitrification and sponge iron supplements heterotrophic denitrification process
Middle electron donor is insufficient, to which guarantee system has efficient nitric efficiency.Meanwhile system generates Fe with sponge iron rot2+、
Fe3+And its based on the chemical dephosphorization effect of hydrolysate, collaboration biological phosphate-eliminating is acted on the phosphorus ligands in water.Therefore, SCSC-S-
Fe techniques can synchronize dephosphorization process with the low C/N of efficient hardening than Tailwater Depth denitrogenation.
Strengthening the particular content of advanced nitrogen dephosphorization is：As shown in Fig. 1, SCSC-S-Fe systems are by organic glass material
Two column of concatenated A, B forms, pillar internal diameter 19cm, height 110cm.Volume enlargement can be controlled diameter height not in Practical Project
Less than 1:3, and internal diameter is not easy to be less than 10cm, otherwise easily blocks reactor.A column water flow modes use upward flow, B column water flow modes
Using lower to stream.
A columns are heterotrophic denitrification denitrogenation filter column.It is 2 that corncob, which is first cut into the ratio between length, width and height,:1:1~3:1:1 it is small
Cuboid, volume are 2~8cm3；It is that 1.5% sodium hydroxide solution impregnates (3~10) h to use mass fraction again；Then clear with clear water
It washes 3~5 times, is dried in 60 DEG C of baking ovens；Processed corncob is finally rolled into spherical shape by nylon mesh, diameter 4~
5cm, packed height are controlled in A pillar height degreeFilling excessively easily cause water outlet COD it is excessively high, filling it is very few easily cause it is de-
Nitrogen treatment effeciency declines.
B columns are sulphur Iron-complex-filling denitrogenation dephosphorizing filter column.Lower layer uses the lime stone that grain size is 5~8mm to load as filtering
Layer, effective height are 25~40cm.Upper layer mass ratio is 2:3 grain size is that 2~3mm sulphur and grain size 3~5mm sponge iron are multiple
It closes filler to load, effective height is controlled in 45~65cm；Sulphur Iron-complex-filling excessively easily causes water outlet TFe concentration and increases, very few
Then dephosphorization efficiency declines.
During above-mentioned denitrogenation dephosphorizing, microorganism by cellulose degradation in corncob in A columns at organic matter, while for A,
Heterotrophic denitrification provides organic carbon source in B columns, and heterotrophic denitrification is occupied an leading position in system, sulphur autotrophic denitrification and sponge iron
Denitrification make up the deficiency of electron donor during heterotrophic denitrification；System has heterotrophic denitrification and autotrophic denitrification
Machine combines, to improve denitrification denitrogenation effect.The organic acid and sulphur autotrophy generated during cellulose degradation in corncob is anti-
The H that nitrifying process generates+, cooperate with dissolved oxygen, nitrate nitrogen, micro- carbon iron primary battery, collectively promote sponge iron rot；Corrosion generates
Fe2+、Fe3+And its hydrolysate Fe (OH)2、Fe(OH)3, FeOOH is to PO4 3-It sweeps, flocculate with volume, adsorption precipitation effect, with
FePO4With multinuclear di iron precipitation form by phosphorus ligands；In addition, there is also biological phosphate-eliminating effects in SCSC-S-Fe systems.
Corncob coupling sulphur Iron-complex-filling after alkali process is formed SCSC-S-Fe process systems by the present invention.Operation control
Condition processed is：HRT is in 6h or more, and temperature is at 15 DEG C or more.In embodiment experiment, control hydraulic detention time HRT is 9h, temperature
Degree is that dynamic filter tank operation test has been carried out at 25 DEG C, investigates the low C/N Tailwater Depths denitrogenation dephosphorizing effect of SCSC-S-Fe system hardenings
Fruit.Experimental result：SCSC-S-Fe system TN, TP average removal rates are respectively 90.41% and 86.98%.SCSC-S-Fe systems
Realize that low C/N synchronizes the purpose of dephosphorization than Tailwater Depth denitrogenation.The present invention is for realizing that low C/N is removed than Tailwater Depth denitrogenation synchronization
Phosphorus and raising recycled water quality have good application prospect.
Description of the drawings
Fig. 1 SCSC-S-Fe reactor assembling assumption diagrams；
Wherein SCSC-S-Fe reactors assembling assumption diagram accessory is as follows：1, water distribution pond；2, water pump 3, water inlet；
4, lime stone；5, sulphur and sponge iron mixed fillers；6, intermediate water tank；7, water pump；8, sample tap；9, water distribution orifice plate；10, at alkali
Corncob after reason；11, cobblestone；12, water outlet；13, water inlet；14, backwash water inlet
Fig. 2 example SCSC-S-Fe system TN, TP removal rates；
Fig. 3 example SCSC-S-Fe systems are discharged NO3 --N、NO2 --N、NH4 +- N concentration；
Fig. 4 example SCSC-S-Fe system Inlet and outlet water pH value and water outlet COD, SO4 2-Concentration；
Fig. 5 example SCSC-S-Fe systems are discharged TP, TFe concentration.
Insoluble product ingredient XRD diagram in Fig. 6 example SCSC-S-Fe systems.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and following instance is intended to illustrate invention, not
It limits the scope of the invention.
The present invention is mainly suitable for handle low C/N than municipal sewage plant's Tailwater Depth denitrogenation dephosphorizing.
It is above-mentioned HRT=9h, temperature be 25 DEG C under the conditions of, SCSC-S-Fe systems carry out dynamic experiment.In conjunction with water outlet COD
Concentration, SO4 2-The total iron of concentration, dissolubility (TFe) concentration and insoluble product X-ray diffractogram (XRD) analyze SCSC-S-Fe
The effect and its mechanism of the Tailwater Depth denitrogenation dephosphorizing of process strengthening low ratio of carbon to ammonium.
Embodiment
A certain amount of KNO is added in test water in tap water3And KH2PO4.It is as follows to control TN, TP concentration：ρ (TN)=ρ
(NO3- N)=35mg.L-1, ρ (H2PO4- P)=1.5mg.L-1.Use 1molL simultaneously-1Hydrochloric acid and 1molL-1Sodium hydroxide
The pH value that solution adjusts water distribution maintains 6.8~7.2.
Reactor is as shown in Fig. 1.The NaOH solution that wherein corncob mass fraction is 1.5% impregnates 10h, cuts into
A length of 2~the 3cm of size, the small rectangle that width is 1~2cm；The grain size of sponge iron is 5~8mm, and the grain size of sulphur is 2~3mm.
Seed sludge comes from Beijing sewage treatment plant returned sludge.
Under the above embodiment, SCSC-S-Fe techniques are applied to municipal sewage plant's Tailwater Depth denitrogenation dephosphorizing
In the process, intensified denitrification and dephosphorization effect, water outlet TN, TP mean concentration is respectively 3.31mgL-1And 0.24mgL-1, it is less than
《Urban sewage reutilization water for scenic environment use water quality》(GB-T18921-2002) TN concentration 15mgL in standard-1It is dense with TP
Spend 1.0mgL-1.This method is suitable for strengthening municipal sewage plant's Tailwater Depth Nitrogen/Phosphorus Removal apparent.
Embodiment particular content is：Experimental provision is as shown in Fig. 1.SCSC-S-Fe process structures are as shown in Fig. 1：A columns
Corncob packed height after middle alkali process is 50cm；Sulphur Iron-complex-filling and lime stone filter layer packed height difference in B columns
For for 50cm and 40cm.Start reactor under the conditions of (15~20) DEG C, waits NO in being discharged3 -- N concentration variable quantities are in 3mgL-1
When interior, show that reactor is stable.Measure Inlet and outlet water NO3 --N、NO2 --N、NH4 +-H、SO4 2-, COD, TN, TP and TFe concentration,
Analyze SCSC-S-Fe process strengthenings municipal sewage plant Tailwater Depth Nitrogen/Phosphorus Removal.The result shows that：As shown in Fig. 2,
TN, TP average removal rate of SCSC-S-Fe techniques are respectively in 90.41% and 86.98%；As shown in attached drawing 3,4,5, it is discharged NO3 --
N、NO2 -- N and NH4 +- H mean concentrations are respectively 0.2mgL-1、1.01mg·L-1And 2.16mgL-1, water outlet TP, TFe,
SO4 2-It is respectively 0.24mgL with COD mean concentrations-1、1.25mg·L-1、92.7mg·L-1And 10.37mgL-1；Such as attached drawing 6
Shown, insoluble product ingredient is mainly FeS, FeOOH, Fe in SCSC-S-Fe systems3O4、Fe6(OH)12(CO3)、Fe3
(PO4)2(OH)2、Fe3(PO4)2·χH2O、FePO4Deng.
It is as follows to analyze the system denitrogenation dephosphorizing mechanism：System is based on heterotrophic denitrification denitrification, sulphur autotrophic denitrification
Supplemented by denitrification with sponge iron, collective effect removes low C/N than the nitrogen in tail water.Sulphur autotrophic denitrification generates simultaneously
H+Organic acid is generated in the process with cellulose degradation, and collaboration dissolved oxygen, nitrate nitrogen, elemental sulfur and carbon iron primary battery promote jointly
Into the corrosion of sponge iron.Corrode the Fe generated2+、Fe3+And their hydrolysate product Fe6(OH)12(CO3) and the substances such as FeOOH,
It sweeps, flocculate by volume, suction-operated is by PO4 3-It is converted to Fe3(PO4)2·χH2O、FePO4And Fe3(PO4)2(OH)2Precipitation；This
Outside, with sponge iron chemical action generation FeS occurs for elemental sulfur, and FeS is first by PO4 3-Its surface is adsorbed, FeS solubility products are recycled
(Ksp=6.3 × 10-18) it is more than FePO4Solubility product (Ksp=1.3 × 10-22), FeS is converted into the FePO of more indissoluble4Precipitation,
Thus by phosphorus ligands.
Claims (1)
1. it is a kind of based on low C/N than recycled water advanced nitrogen phosphorus removing method, it is characterised in that：To fill the corn after alkali process
Core is that denitrification denitrogenation filter column is known as A columns, and filling quality ratio is 2 in series connection:The denitrogenation dephosphorizing of 3 sulphur and sponge iron mixed fillers
Filter column is known as B columns；A column water flow modes use upward flow, and B column water flow modes are using lower to stream；
It is 2 that corncob, which is first cut into the ratio between length, width and height, in A columns:1:1~3:1:1 small cuboid, volume are 2~8cm3；It uses again
The sodium hydroxide solution that mass fraction is 1.5% impregnates 3~10h；Then it is cleaned 3~5 times with clear water, is dried in 60 DEG C of baking ovens
It is dry；Processed corncob is finally rolled into spherical shape, 4~5cm of diameter by nylon mesh, packed height is controlled in A pillar height degree
's
B columns lower layer uses the lime stone that grain size is 5~8mm to load as filter layer, and effective height is 25~40cm；Upper layer quality
Than being 2:3 grain size is that 2~3mm sulphur and grain size 3~5mm sponge Iron-complex-fillings load, effective height control 45~
65cm。
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