CN105923757A - Method for phosphorus removal and denitrification through iron elementary substance cooperating with sulfur autotrophic denitrification - Google Patents
Method for phosphorus removal and denitrification through iron elementary substance cooperating with sulfur autotrophic denitrification Download PDFInfo
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- CN105923757A CN105923757A CN201610313473.6A CN201610313473A CN105923757A CN 105923757 A CN105923757 A CN 105923757A CN 201610313473 A CN201610313473 A CN 201610313473A CN 105923757 A CN105923757 A CN 105923757A
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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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Abstract
The invention provides a method for phosphorus removal and denitrification through iron elementary substance cooperating with sulfur autotrophic denitrification. The method is characterized in that scrap iron is doped into a sulfur/limestone combined packed bed reactor, the iron elementary substance is oxidized by hydrogen ions (H+) generated through sulfur autotrophic denitrification, iron ions dissolved out and phosphate radicals form insoluble precipitate, and the insoluble precipitate is retained by a packed bed for enhanced phosphorus removal. Phosphorus is chemically removed based on the iron elementary substance cooperating with sulfur autotrophic denitrification, the phosphorus removal effect is good and stable, H+ generated through sulfur autotrophic denitrification can be consumed, the capacity for buffering pH of the system is enhanced, and the raw materials including sulfur and the iron elementary substance are cheap and easy to obtain.
Description
Technical field
The invention belongs to sewage treatment area, be specifically related to a kind of ferrum simple substance and work in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation
Method.
Background technology
Body eutrophication is a global phenomenon in recent decades, is affected by mankind's activity, river, lake
The increase of the discharge capacity of the water body Middle nutrition elements such as pool is allowed to tend to eutrophication.During water body generation eutrophication,
Some algae breaks out, and causes water quality anoxia to deteriorate, and is full of fish bad smell everywhere, destroys water ecosystem
Stability, and have a strong impact on urban water supply and drinking water safety.The basic origin cause of formation of body eutrophication is nutrition unit
Element nitrogen and the increase of phosphorus, in order to solve the problem of body eutrophication, by the end of 2013, the built city of China
Town sewage treatment plant more than 5000 seat.It is (main that urban wastewater treatment firm biochemical treatment can cut down major part pollutant
If Organic substance), but the aqueous concentration of total nitrogen and total phosphorus is the highest, and the biochemical treatment of town sewage plant is not
Being the basic scheme of solution problem, it can only play the effect delayed.In the world it is generally believed that total nitrogen in water body
Concentration 0.2mg/L, total phosphorus concentration 0.02mg/L are the marginal values of body eutrophication.In order to improve by Na Shui
The quality of water environment of body, it would be highly desirable to the nitrogen in sewage and phosphorus are carried out advanced treating.
Denitrogenation technology based on heterotrophic denitrification, owing to denitrification percent is high, process route is the most ripe, so by extensively
General for wastewater biological denitrificaion field.But heterotrophic denitrification denitrogenation technology be applied to into water organic loading relatively low
During the two stage treatment technique that (the most southern low carbon-nitrogen ratio sewage), subsoil water and municipal wastewater process, can go out
The phenomenon that existing carbon source is not enough.When organic loading of intaking is relatively low, it is necessary to additionally add Organic substance to provide carbon source
Thus cause the increase of operating cost.When adding Organic substance, run into the situation that variation water quality is bigger, the most not
Can add accurately, can cause waste and affect effluent quality when adding excess, during dosage deficiency, denitrogenation reaches
Less than preferable effect.
For above-mentioned reasons, autotrophic denitrification receives more and more attention.Autotrophic denitrification is primarily referred to as relying on
Inorganic matter (such as hydrogen, sulfur) is as electron donor, with inorganic carbide compound (such as CO2、HCO3 -)
Carbon source as microbial metabolism carrys out denitrogenation.When hydrogen is as electron donor, due to hydrogen dissolubility in water
Ratio is relatively low, thus causes its utilization ratio low, and hydrogen is explosive combustibles, and shipping storage is the most inconvenient,
Production cost is higher, and its actual application is very limited.By contrast, sulfur autotrophic denitrification technique is due to instead
Nitrification efficiency is high, Sulfur price is cheap, raw material is suitable for acquisition, operating mode stable and sludge yield is low,
The aspects such as transport and use are more safe and convenient and become the focus of research.
But sulfur autotrophic denitrification technique is being removed in water while nitrate nitrogen, to the removal effect of total phosphorus and pay no attention to
Think, be generally unable to reach synchronous nitrogen and phosphorus up to standard.Therefore can be in the way of using synchronization dephosphorization, strengthening sulfur autotrophy is anti-
The phosphor-removing effect of nitration processes.
Prior art CN101973629A provides a kind of pyrite method as biochemical filler denitrogenation dephosphorizing,
For the synchronous denitrification dephosphorizing of low carbon-nitrogen ratio sewage, its ultimate principle is that thiobacillus denitrificans utilizes bearing in pyrite
Divalent sulfur carries out autotrophic denitrification as electron donor, and the ferrous ion of pyrite dissolution and phosphate radical formed heavy
Shallow lake dephosphorization, it is achieved thereby that denitrification and phosphorus removal integration.But owing to pyrite dissolubility in water is relatively low, meeting
The dissolution rate of the negative divalent sulfur of impact, so that response speed is slow.
Summary of the invention
The problem existed in view of prior art, the invention provides a kind of ferrum simple substance and works in coordination with the sulfur autotrophic denitrification degree of depth
Dephosphorization and denitrification process, including: in sulfur/limestone combination packed bed reactor, fill iron filings, pass through sulfur
Autotrophic denitrification effect produces substantial amounts of hydrion (H+), H+Reacting with ferrum simple substance can dissolution iron ion (bivalence
Iron ion and ferric ion, account for leading with ferric ion), then iron ion and phosphate radical reaction generate not
Molten precipitate, is filled bed and retains removal.
Wherein, sulfur/limestone combination packed bed is made up of sulfur and limestone particle, limestone and sulfur
Mass ratio 0.5～1.5:1.Limestone is graininess, and particle diameter is 1～10mm；Sulfur is graininess, and particle diameter is
1～10mm.
Mixing iron filings in sulfur/limestone combination packed bed reactor, iron filings with the mass ratio of sulfur are
0.01～0.5:1.
In sulfur/limestone combination packed bed reactor, the pH of water inlet is 6.0～8.5.
Sulfur, limestone, iron filings mix homogeneously, be filled into packed bed, containing nitrate anion and phosphatic waste water warp
Cross packed bed processed after, drain from outlet.
Further preferably water inlet uses the mode of upward flow, and water inlet is positioned at the downside of packed bed reactor, water outlet
Mouth is positioned at the upside of packed bed reactor.
Or to the mode of stream under water inlet employing, water inlet is positioned at the upside of packed bed reactor, and outlet is positioned at
The downside of packed bed reactor.
Carry out backwash when the loss of flood peak combining packed bed reactor exceedes design maximum head loss, will fill out
Fill the phosphorous precipitate in bed to remove, recover disposal ability.
The described loss of flood peak refers to current loss of the energy of unit mass liquid in motor process.
And downside at packed bed reactor is provided with backwash trachea and backwash water pipe further.By this
Design and carry out backwash when the loss of flood peak combining packed bed reactor exceedes design maximum head loss, can be by
Phosphorous precipitation in packed bed is removed, and recovers disposal ability.
The present invention includes relative to beneficial effect produced by prior art:
1, in technique of the present invention use sulfur and ferrum simple substance low price, raw material be suitable for acquisition,
Operating mode is stable and sludge yield is low.
2, technology utilization ferrum simple substance of the present invention is worked in coordination with sulfur autotrophic denitrification and is carried out chemical dephosphorization, can disappear
The H produced during consumption sulfur autotrophic denitrification+, the strengthening system buffer capacity to pH.
3, technology utilization ferrum simple substance of the present invention is worked in coordination with sulfur autotrophic denitrification and is carried out chemical dephosphorization, Ke Yida
Effect to strengthening chemical dephosphorization.
4, ferrum simple substance and H+The iron phosphate that the reaction iron ion of dissolution and phosphate radical reaction produce can by sulfur/
Limestone combination packed bed reactor retains removal, is recovered the interception capacity of packed bed by backwash.
Accompanying drawing explanation
Fig. 1 one of the present invention sulfur/limestone combination packed bed reactor device schematic diagram (water inlet use to
The mode of stream)
Fig. 2 water inlet is the phosphor-removing effect under the conditions of difference hydraulic detention time (HRT) during Sewage Plant secondary effluent
Fig. 3 one of the present invention sulfur/limestone combination packed bed reactor device schematic diagram (water inlet use under to
The mode of stream)
Before and after Fig. 4 present invention fills ferrum simple substance, phosphor-removing effect compares schematic diagram
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the embodiment of invention is not
It is limited to this.
Embodiment one:
A kind of method that ferrum simple substance works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, at sulfur/limestone combination packed bed
In reactor, fill iron filings, produce substantial amounts of H by sulfur autotrophic denitrification effect+, H+React with ferrum simple substance
Meeting dissolution iron ion, then iron ion and phosphate radical reaction form insoluble precipitate, are filled bed and retain removal.
A kind of sulfur/limestone combination packed bed reactor, installation drawing is as shown in Figure 1.Sulfur/limestone combination
The packing layer of packed bed is sulfur and limestone, limestone and the mass ratio 1.37:1 of sulfur.Limestone particle grain
Footpath is 2～3mm, and drusen particle diameter is 3～5mm.Sulfur/limestone combination packed bed reactor is mixed
Entering iron filings, iron filings are 0.026:1 with the mass ratio of sulfur.Sulfur/limestone combination packed bed reactor is intake
PH be 6.5.Packed bed reactor device uses the mode of upward flow water inlet, so not only contributes to anti-nitre
The spilling of the gas produced during change, and be conducive to creating anaerobic environment, the most denitrifying generation.Work as group
The loss of flood peak of conjunction packed bed reactor carries out backwash when exceeding design maximum head loss, and backwash uses gas
Water combines the mode of recoil, and reactor returns to initial treatment effect by after backwash.
Water inlet is Shenzhen's secondary effluent from sewage treatment plant, and total phosphorus is about 1.00mg/L.Respectively at HRT=1
The phosphor-removing effect of h and HRT=0.5h is as shown in Figure 2.It can be seen that the secondary effluent of certain Sewage Plant
(total phosphorus concentration is about 1.00mg/L), after the combination packed bed reactor of the present invention processes, water outlet is total
Phosphorus concentration is 0.05～0.15mg/L, and the clearance of total phosphorus is 85～95%, and secondary effluent can be made to mark from one-level B
Standard carries mark to surface water IV standard.
In combinations thereof packed bed reactor, it is monitored finding to the pH value of Inlet and outlet water: water inlet pH value
6.89～7.27, the pH value of water outlet is 6.88～7.29, and Inlet and outlet water pH value is more or less the same.Illustrate to fill iron filings
Afterwards, iron filings and limestone can neutralize the hydrion produced in the middle of sulfur autotrophic denitrification process, and sulfur completely
By contrast, the buffer capacity of acid is strengthened/limestone combination packed bed reactor by this system.
Embodiment two:
A kind of method that ferrum simple substance works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, at sulfur/limestone combination packed bed
In reactor, fill iron filings, produce substantial amounts of H by sulfur autotrophic denitrification effect+, H+React with ferrum simple substance
Meeting dissolution iron salt, then iron ion and phosphate radical reaction form insoluble precipitate, are filled bed and retain removal.
A kind of sulfur/limestone combination packed bed reactor, installation drawing is as shown in Figure 3.Sulfur/limestone combination
The packing layer of packed bed is sulfur and limestone, limestone and the mass ratio 0.69:1 of sulfur.Limestone particle grain
Footpath is 3～5mm, and drusen particle diameter is 5～7mm.Sulfur/limestone combination packed bed reactor is mixed
Entering iron filings, iron filings are 0.05:1 with the mass ratio of sulfur.Water inlet in sulfur/limestone combination packed bed reactor
PH is 8.To the mode flowing to water under the employing of packed bed reactor device.Water when combination packed bed reactor
Head loss carries out backwash when exceeding design maximum head loss, and backwash uses air water to combine the mode of recoil,
Reactor returns to initial treatment effect by after backwash.
The industrial wastewater that water inlet is certain factory, total phosphorus is about 15.00mg/L, through the combination filling of the present invention
After bed reactor for treatment, water outlet total phosphorus concentration is 1.5～3mg/L, and the clearance of total phosphorus is 80～90%.
Comparative example one:
In sulfur/limestone combination packed bed reactor, contrast with or without admixture ferrum simple substance, the dephosphorization effect of system
Really.In the case of two kinds, Fig. 4 is shown in the removal effect of total phosphorus.As shown in Figure 4, before not filling ferrum simple substance,
The water inlet of total phosphorus and water outlet mean concentration are respectively 1.08mg/L and 0.99mg/L, and average removal amount is 0.09
Mg/L, average removal rate is 8.3%；After admixture ferrum simple substance, the water inlet of total phosphorus and water outlet mean concentration are 1.03
Mg/L and 0.09mg/L, average removal amount is 0.94mg/L, and it is 91.2% that average removal rate increases to, and adds
After ferrum simple substance, the effect of reinforced phosphor-removing is it is obvious that total phosphorus can reach surface water IV class water from the water outlet of one-level B.
This is because the removal effect of total phosphorus mainly relies on Ca2+Chemical precipitation, due to factors such as pH value
Impact, the removal effect of total phosphorus is unsatisfactory；After admixture ferrum simple substance, dephosphorization function relies primarily on iron ion
Chemical precipitation, phosphor-removing effect is notable.
Above content is to combine the further details of explanation that the present invention is done by concrete preferred implementation,
But do not indicate that the present invention be embodied as be limited to these explanations.For restraining the general of neck belonging to the present invention
For logical technical staff, without departing from the inventive concept of the premise, it is also possible to make some simple deductions or
It is to replace, is regarded as belonging to protection scope of the present invention.
Claims (10)
1. the method that a ferrum simple substance works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is characterised in that including: sulfur/
In limestone combination packed bed reactor, fill iron filings, produce H by sulfur autotrophic denitrification effect+, H+With
Ferrum simple substance reaction meeting dissolution iron ion, then iron ion and phosphate radical reaction generate insoluble precipitate, are filled bed
Retain removal.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: packing layer is made up of sulfur and limestone particle, limestone and the mass ratio 0.5～1.5:1 of sulfur.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levying and be: limestone is graininess, particle diameter is 1～10mm；Sulfur is graininess, and particle diameter is 1～10mm.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: mixing iron filings in sulfur/limestone combination packed bed reactor, iron filings with the mass ratio of sulfur are
0.01～0.5:1.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: in sulfur/limestone combination packed bed reactor, the pH of water inlet is 6.0～8.5.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: sulfur, limestone, iron filings mix homogeneously, be filled into packed bed, containing nitrate anion and phosphatic useless
Water, after packed bed is processed, is drained from outlet.
The method that a kind of ferrum simple substance the most according to claim 6 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: water inlet uses the mode of upward flow, and water inlet is positioned at the downside of packed bed reactor, and outlet is positioned at
The upside of packed bed reactor.
The method that a kind of ferrum simple substance the most according to claim 6 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: to the mode of stream under water inlet employing, water inlet is positioned at the upside of packed bed reactor, and outlet is positioned at
The downside of packed bed reactor.
The method that a kind of ferrum simple substance the most according to claim 1 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: carry out backwash when the loss of flood peak combining packed bed reactor exceedes design maximum head loss,
Phosphorous precipitate in packed bed is removed, recovers disposal ability.
The method that a kind of ferrum simple substance the most according to claim 9 works in coordination with sulfur autotrophic denitrification dephosphorization denitrogenation, it is special
Levy and be: the downside at packed bed reactor is provided with backwash trachea and backwash water pipe further.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517649A (en) * | 2016-11-14 | 2017-03-22 | 江南大学 | Sewage deep dentrification and dephosphorization method |
| CN107522286A (en) * | 2017-10-17 | 2017-12-29 | 浙江深德环境技术有限公司 | A kind of tail water processing method based on sulphur/oyster shell |
| CN110746036A (en) * | 2019-09-29 | 2020-02-04 | 郑州大学 | Low-carbon-source sewage autotrophic denitrification deep denitrification device and method |
| CN110921811A (en) * | 2019-11-29 | 2020-03-27 | 南京华创环境技术研究院有限公司 | Modified volcanic rock filler and preparation method and application thereof |
| CN111137973A (en) * | 2019-12-16 | 2020-05-12 | 清上(苏州)环境科技有限公司 | Denitrification functional filler, filler ball, filling method and application |
| CN111977787A (en) * | 2020-08-10 | 2020-11-24 | 深圳市播绿者生态科技股份有限公司 | Self-activated denitrification carrier material and preparation method and application thereof |
| CN114524513A (en) * | 2022-01-28 | 2022-05-24 | 大连理工大学 | Method for treating low C/N sewage by anaerobic-aerobic-anoxic-moving bed autotrophic denitrification process |
| CN115353198A (en) * | 2022-07-21 | 2022-11-18 | 北京工业大学 | Synchronous nitrogen and phosphorus removal method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517649A (en) * | 2016-11-14 | 2017-03-22 | 江南大学 | Sewage deep dentrification and dephosphorization method |
| CN106517649B (en) * | 2016-11-14 | 2020-01-21 | 江南大学 | Method for deep nitrogen and phosphorus removal of sewage |
| CN107522286A (en) * | 2017-10-17 | 2017-12-29 | 浙江深德环境技术有限公司 | A kind of tail water processing method based on sulphur/oyster shell |
| CN110746036A (en) * | 2019-09-29 | 2020-02-04 | 郑州大学 | Low-carbon-source sewage autotrophic denitrification deep denitrification device and method |
| CN110746036B (en) * | 2019-09-29 | 2022-04-19 | 郑州大学 | Low-carbon-source sewage autotrophic denitrification deep denitrification device and method |
| CN110921811A (en) * | 2019-11-29 | 2020-03-27 | 南京华创环境技术研究院有限公司 | Modified volcanic rock filler and preparation method and application thereof |
| CN111137973A (en) * | 2019-12-16 | 2020-05-12 | 清上(苏州)环境科技有限公司 | Denitrification functional filler, filler ball, filling method and application |
| CN111977787A (en) * | 2020-08-10 | 2020-11-24 | 深圳市播绿者生态科技股份有限公司 | Self-activated denitrification carrier material and preparation method and application thereof |
| CN114524513A (en) * | 2022-01-28 | 2022-05-24 | 大连理工大学 | Method for treating low C/N sewage by anaerobic-aerobic-anoxic-moving bed autotrophic denitrification process |
| CN115353198A (en) * | 2022-07-21 | 2022-11-18 | 北京工业大学 | Synchronous nitrogen and phosphorus removal method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter |
| CN115353198B (en) * | 2022-07-21 | 2023-09-19 | 北京工业大学 | Synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter |
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Application publication date: 20160907 |