CN109650560A - A kind of denitrification filter pool composite filling and its application - Google Patents
A kind of denitrification filter pool composite filling and its application Download PDFInfo
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- CN109650560A CN109650560A CN201910141111.7A CN201910141111A CN109650560A CN 109650560 A CN109650560 A CN 109650560A CN 201910141111 A CN201910141111 A CN 201910141111A CN 109650560 A CN109650560 A CN 109650560A
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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
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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
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Biodiversity & Conservation Biology (AREA)
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a kind of denitrification filter pool composite filling and its applications, wherein composite filling includes iron carbon filler, sulphur and porous material.It include reduced iron powder, active carbon, copper powder, pore creating material, pore creating material and pH adjusting agent in the iron carbon filler.Filler sequence in denitrification combination of the present invention filter tank is respectively iron carbon filler, sulphur and porous material from top to bottom.Iron-carbon micro-electrolysis can be generated in water by iron carbon filler, the ferrous iron and reproducibility hydrogen of generation are by nitrate-nitrogen reduction at nitrogen, while denitrifying bacterium, using hydrogen and sulphur as electron donor, reduction adds organic carbon source, to realize autotrophic denitrification.The composite filling biofilm speed is fast simultaneously, and nitrogen removal performance is good under optimum operation technological parameter, and from a wealth of sources, and price is inexpensive.The present invention solves the problems, such as the problem of pH is excessively high or too low in reactor and nitrite nitrogen is accumulated, and have good removal effect by the combination of different fillers.
Description
Technical field
The present invention relates to nitrogenous sanitary sewage and technology for treating industrial waste water, espespecially a kind of denitrification filter pool composite filling and
It is applied.
Background technique
With the development of economy, since human living standard improves and agrochemical excessively the reasons such as uses, so that
A large amount of nitrogenous sanitary sewage and industrial wastewater are discharged into water body, and the exceeded of nitrogen content can cause water eutrophication, and can turn
It turns to " three cause " substance nitrite and seriously threatens the health of the mankind.Therefore it researchs and develops at economic, efficient denitrogenation of waste water
Reason technology, it has also become the emphasis and hot spot in Water Pollution Control Engineering field.In numerous denitrogenation technologies, bio-denitrification technology tool
There is economy, efficiently and not generate the characteristics of secondary pollution, the research of the denitrification function of anaerobic reactor is had become in recent years
For hot spot.
The main function of filler be accommodate attached microbial, be microorganism growth carrier, provided for microorganism inhabit with
The stable environment of breeding, inner surface abundant provide the surface and inner space of attachment for microorganism, make reactor as far as possible
Keep more microbial biomass.Meanwhile filler has enforceable turbulent fluctuation to act on water flow, and water flow is enable to redistribute, and changes
Its flow direction, so that water flow be made to more uniformly spread under reactor cross-section.Filler has the suspended matter in water certain
Crown_interception.Due to, with the presence of filler, greatly reducing the concentration of suspended matter in water outlet in reactor.Therefore, filler is in sewage
Effect in treatment process is particularly significant.Therefore, developing suitable biologic packing material is to lead in water process in bio-denitrification technology future
The premise that domain promotes and applies.
In traditional autotrophic denitrification reactor, people are single by iron autotrophic denitrification technology or the anti-nitre of sulphur autotrophy
Change technology carries out denitrogenation.Wherein merely by iron autotrophic denitrification technology, meeting when iron carbon filler generates galvanic interaction in water
Generate a large amount of OH-, so that the pH in water constantly rises, be not suitable for the existence of microorganism；Similarly, pass through the anti-nitre of sulphur autotrophy merely
A large amount of H can be generated when changing reaction+, and the SO4 of high concentration2-It will cause the accumulation of nitrite.
Summary of the invention
It is described in order to solve the above-mentioned technical problems, the present invention provides a kind of denitrification filter pool composite filling and its application
Filler is specially the composite filling that a kind of low-carbon-source for low C/N wastewater biological denitrificaion technology adds efficient denitrification filter pool.
Iron-carbon micro-electrolysis can be generated in water by iron carbon filler, the ferrous iron and reproducibility hydrogen of generation are by nitrate-nitrogen reduction at nitrogen
Gas, while denitrifying bacterium, using hydrogen and sulphur as electron donor, reduction adds organic carbon source, to realize the anti-nitre of autotrophy
Change.The composite filling biofilm speed is fast simultaneously, and nitrogen removal performance is good under optimum operation technological parameter, and from a wealth of sources, price valence
It is honest and clean.
The present invention solves the problems, such as that pH is excessively high or too low in reactor, was testing by the combination of different fillers
The accumulation of nitrite nitrogen is not found in journey, and has good removal effect.The design of the invention is scientific and reasonable, overcomes traditional life
Object denitrogenation technology takes up a large area, needs the shortcomings that a large amount of additional carbons.
In order to reach the object of the invention, the present invention provides a kind of denitrification filter pool composite fillings, comprising: iron carbon filler,
Sulphur, porous material and pH padded coaming.Optionally, the denitrification filter pool composite filling is by iron carbon filler, sulphur, porous
Material and pH padded coaming composition.
In denitrification filter pool composite filling provided by the invention, the iron carbon filler includes following component: reduced iron powder, work
Property charcoal, copper powder, binder, pore creating material and pH adjusting agent.Optionally, the iron carbon filler is by reduced iron powder, active carbon, copper
Powder, binder, pore creating material and pH adjusting agent composition.
In denitrification filter pool composite filling provided by the invention, the iron carbon filler each component mass ratio are as follows: reduced iron powder
40-45%, active carbon 12-15%, copper powder 8-10%, binder 20-25%, pore creating material 5-8% and pH adjusting agent 5-8%；
Optionally, the reduced iron powder 45%, active carbon 15%, copper powder 10%, binder 20%, pore creating material 5%, pH tune
Save agent 5%.
In denitrification filter pool composite filling provided by the invention, the binder is selected from calcium sulfate, sodium alginate, Arab
One of glue and polyvinyl alcohol are a variety of；
In denitrification filter pool composite filling provided by the invention, the pH adjusting agent be selected from sodium bicarbonate, sodium dihydrogen phosphate,
One of sodium hydroxide and calcium carbonate are a variety of；
In denitrification filter pool composite filling provided by the invention, the pore creating material is selected from ammonium hydrogen carbonate.
In denitrification filter pool composite filling provided by the invention, the partial size of the reduced iron powder is 150-200 mesh, the work
Property charcoal partial size be 150-200 mesh, the partial size of the copper powder is 150-200 mesh.
In denitrification filter pool composite filling provided by the invention, the iron carbon filler is spherical shape, diameter 9-12mm.
In denitrification filter pool composite filling provided by the invention, the filler sequence of the composite filling is respectively from top to bottom
Iron carbon filler, sulphur, pH padded coaming and porous material；
In denitrification filter pool composite filling provided by the invention, the iron carbon filler, sulphur, pH padded coaming and porous
The volume ratio of material is 1-3:1-3:0-2:1-2, and the composite filling packed height is the 50-80% of anaerobic reactor height.
In denitrification filter pool composite filling provided by the invention, the porous material be selected from medical stone, zeolite, haydite, with
And one or more of volcanic rock；The pH padded coaming is selected from one or both of oyster shell and lime stone.
In denitrification filter pool composite filling provided by the invention, the partial size of the porous material is 3-5mm；The pH buffering
The partial size of material is 3-5mm；The partial size of the sulphur is 0.5-1mm.
In denitrification filter pool composite filling provided by the invention, the preparation method of above-mentioned iron carbon filler, including following step
It is rapid:
(1) by the reduced iron powder, active carbon, copper powder, binder, pore creating material and pH adjusting agent blending and mixing, slowly
The water that material quality 15-20% is added is mixed to form mixture of viscous form；
(2) mixture obtained in step (1) is filled into mold, 45-60 DEG C in a vacuum drying oven, dry 6-
8h；Wherein optimum efficiency is to be dried in vacuo 8h at 60 DEG C.
(3) the product high-temperature roasting under inert atmosphere gases that will be obtained after vacuum drying in step (2), that is, be made iron carbon
Filler.
Optionally, the preparation method of the iron carbon filler is made of above step.
In the preparation method of iron carbon filler provided by the invention, the inert atmosphere gases are in inert gas or nitrogen
It is one or more；
In the preparation method of iron carbon filler provided by the invention, the condition of the high-temperature roasting is to roast at 400-700 DEG C
Burn 2-4h.Wherein optimum efficiency is to roast 4h at 400 DEG C.
On the other hand, the present invention also provides above-mentioned denitrification filter pool composite fillings to handle nitrogenous sanitary sewage and industry
Application in the anaerobic reactor of waste water.
Iron carbon filler in composite filling in the present invention, medical stone, zeolite, haydite and volcanic rock are porous material, tool
There is good specific surface area, growing environment and attachment point can be provided for microorganism；It is micro- that iron carbon is generated in water by iron carbon filler
Electrolysis, the ferrous iron and reproducibility hydrogen of generation by nitrate-nitrogen reduction at nitrogen, while denitrifying bacterium using hydrogen and sulphur as
Electron donor, to realize autotrophic denitrification.Reduce the dependence to nutrients；Oyster shell has porous structure, is similarly micro-
Biology provides growing environment and attachment point, while the calcium carbonate in oyster shell can neutralize the acid of microbial cultivation process generation
Matter plays a part of adjusting pH value.
It is a further object to provide a kind of application of said combination filler in anaerobic reactor.
In dissolution of the said combination filler provided by the invention in the application of anaerobic reactor, in the anaerobic reactor
Oxygen concentration is 1.0-2.0mg/L, ratio 3 >=C/N >=1.5 of COD concentration and nitrate in sewage；C/N if it is greater than 3,
It will make the heterotrophic denitrifying Bacteria dominance bacterium in reactor, and heterotroph and autotrophic bacterium are competitive relation, at this time autotrophic bacterium
It will reduce, filler is ineffective；
Heterotrophic denitrifying Bacteria, iron autotrophic denitrification bacterium and sulphur autotrophic denitrification bacterium are advantage in the anaerobic reactor
Bacterium, and composite filling surface is formed with stable biomembrane.
Beneficial effects of the present invention:
(1) composite filling provides sufficient space for microorganism attachment, so that having in reactor as much as possible
Microorganism exists.Meanwhile composite filling can also change the flow direction of water flow, so that waste water comes into full contact with microorganism, improve
The removal efficiency of pollutant.
(2) iron powder in composite filling and active carbon formed in water iron-carbon micro-electrolysis reaction, generate reduced form hydrogen [H] and
Ferrous iron, [H] and ferrous iron are by the nitrate-nitrogen reduction of part at nitrogen.
(3) iron plays capture consumption underground oxygen in water as oxygen agent is caught, and creates anaerobism necessary to denitrification process
Environment.
(4) denitrifying bacterium forms the reaction of iron autotrophic denitrification and sulphur autotrophy using hydrogen and elemental sulfur as electron donor
Anti-nitration reaction denitrogenation reduces adding for sulphur organic carbon source, reduces costs.Simultaneously as the autotrophic denitrification bacterium generation cycle
Long, sludge yield is few, avoids the generation of sludge bulking phenomenon.
(5) by the reaction of iron autotrophic denitrification and sulphur autotrophic denitrification reaction bonded, the alkali generated in iron-carbon micro-electrolysis can be with
Neutralization reaction occurs with the acid generated in sulphur autotrophic denitrification, the acid-base balance in reactor is maintained, so that the pH in reactor
Stablize in the range for being suitble to denitrifying bacterium growth.
(6) in actual sewage when ratio C/N >=1.5 of COD concentration and nitrate, using prepared by the present invention de-
The anaerobic reactor of nitrogen functional stuffing does not need additionally to add carbon source, and autotrophic denitrification can be realized, gone using biochemical process
Except nitrate nitrogen.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by specification, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical solution of the present invention, and constitutes part of specification, with this
The embodiment of application technical solution for explaining the present invention together, does not constitute the limitation to technical solution of the present invention.
Fig. 1 is the nitrate nitrogen removal effect contrast schematic diagram of volcanic rock conventional fillers and composite filling；
Fig. 2 is the nitrate nitrogen removal effect contrast schematic diagram of sulphur filler and composite filling.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to the present invention
Embodiment be described in detail.It should be noted that in the absence of conflict, in the embodiment and embodiment in the application
Feature can mutual any combination.
By specific embodiment, clear, complete description is carried out to technical solution of the present invention.
The embodiment provides a kind of denitrification filter pool composite fillings, comprising: iron carbon filler, sulphur, porous material
Material and pH padded coaming.Optionally, the denitrification filter pool composite filling is by iron carbon filler, sulphur, porous material and pH
Padded coaming composition.
In embodiments of the present invention, the iron carbon filler includes following component: reduced iron powder, active carbon, copper powder, bonding
Agent, pore creating material and pH adjusting agent.Optionally, the iron carbon filler is by reduced iron powder, active carbon, copper powder, binder, pore creating material
And pH adjusting agent composition.
In embodiments of the present invention, the iron carbon filler each component mass ratio are as follows: reduced iron powder 40-45%, active carbon 12-
15%, copper powder 8-10%, binder 20-25%, pore creating material 5-8% and pH adjusting agent 5-8%；
Optionally, the reduced iron powder 45%, active carbon 15%, copper powder 10%, binder 20%, pore creating material 5%, pH tune
Save agent 5%.
In embodiments of the present invention, the binder is in calcium sulfate, sodium alginate, Arabic gum and polyvinyl alcohol
It is one or more；
In embodiments of the present invention, the pH adjusting agent is selected from sodium bicarbonate, sodium dihydrogen phosphate, sodium hydroxide and calcium carbonate
One of or it is a variety of；
In embodiments of the present invention, the pore creating material is selected from ammonium hydrogen carbonate.
In embodiments of the present invention, the iron carbon filler is spherical shape, diameter 9-12mm.
In embodiments of the present invention, the filler sequence of the composite filling is respectively iron carbon filler, sulphur, pH from top to bottom
Padded coaming and porous material；
In embodiments of the present invention, the volume ratio of the iron carbon filler, sulphur, pH padded coaming and porous material is 1-
3:1-3:0-2:1-2, the composite filling packed height are the 50-80% of anaerobic reactor height.
In embodiments of the present invention, the porous material is selected from one of medical stone, zeolite, haydite and volcanic rock
Or it is two or more；The pH padded coaming is selected from one or both of oyster shell and lime stone.
In embodiments of the present invention, used heterotrophic denitrifying Bacteria, iron autotrophic denitrification bacterium and sulphur autotrophic denitrification
Bacterium is derived from the sludge of Beijing Gaobeidian City sewage plant anaerobism concentration basin.
In embodiments of the present invention, used porous material partial size is 3-5mm, and pH padded coaming partial size is 3-5mm, sulphur
Sulphur partial size is 0.5-1mm；
In embodiments of the present invention, used reduced iron powder partial size is 150-200 mesh, activated carbon particle size 150-200
Mesh, copper powder size are 150-200 mesh.
Embodiment 1:
Low-carbon-source in embodiment 1 adds the composite filling of efficient denitrification filter pool, by iron carbon filler, sulphur, porous material
Material composition, wherein each component mass ratio of iron carbon filler is reduced iron powder 45%, active carbon 15%, copper powder 10%, calcium sulfate
20%, ammonium hydrogen carbonate 5%, sodium bicarbonate 5%.
(1) by the reduced iron powder, active carbon, copper powder, calcium sulfate, ammonium hydrogen carbonate and sodium bicarbonate blending and mixing, delay
The slow water that material quality 20% is added is mixed to form mixture of viscous form；
(2) mixture obtained in step (1) is filled into internal diameter is in 9mm spherical die in a vacuum drying oven 60
DEG C, dry 8h；
(3) product obtained after being dried in vacuo in step (2) 400 DEG C of roasting 2h under high pure nitrogen, that is, be made iron carbon
Filler.
(4) the static biofilm stage: composite filling is iron carbon filler, sulphur and volcano made from step (3) from top to bottom
Rock, volume ratio are as follows: iron carbon filler: sulphur: volcanic rock=1:1:2, composite filling accounts for the 50% of reactor volume, and is reacting
Sludge is added in device to be cultivated, makes sludge activity recovery, sludge additional amount, which is subject to, fills reactor, while with hydraulic retention
The water inlet of time HRT=12h, dissolved oxygen DO=1.0-2.0mg/L of intaking, averagely water inlet nitrate are 30 ± 5mg/L, C/N
=1.5-2 is maintained two weeks.
(5) continuous cultivation stage: keeping the hydraulic detention time HRT=8h of reactor, if effluent quality fluctuates small, nitre state
The removal rate of nitrogen tends towards stability, and illustrates that biomembrane has gradually formed and grown stabilization, there is a stronger anti-shock loading, biofilm at
Function.
(6) stable operation stage: being 30 ± 5mg/L, C/N=1.5-2 in average water inlet nitrate, when hydraulic retention
Between HRT=4h, intake dissolved oxygen DO=1.0-2.0mg/L under conditions of, averagely water outlet nitrate be 1.9-2.8mg/L,
The removal rate of nitrate nitrogen is 83-98%, and the accumulation without ammonia nitrogen and nitrite nitrogen, water outlet pH are 6.0-6.3.
Embodiment 2:
Low-carbon-source in embodiment 2 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper is respectively iron carbon filler, sulphur, oyster shell and volcanic rock, volume ratio are as follows: iron carbon filler: sulphur: oyster shell: volcanic rock
=1:1:1:1, composite filling account for the 50% of reactor volume, and wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 1.8-3mg/L, and the removal rate of nitrate nitrogen is 90-94%, and without ammonia nitrogen
With the accumulation of nitrite nitrogen, water outlet pH is 7.0-7.3.
Embodiment 3:
Low-carbon-source in embodiment 3 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper is respectively iron carbon filler, sulphur, medical stone and volcanic rock, volume ratio are as follows: iron carbon filler: sulphur: medical stone: volcanic rock
=1:1:1:1, composite filling account for the 50% of reactor volume, and wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 2.3-3.2mg/L, and the removal rate of nitrate nitrogen is 89-92%, and without ammonia
The accumulation of nitrogen and nitrite nitrogen, water outlet pH are 6.3-6.8.
Embodiment 4:
Low-carbon-source in embodiment 4 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper is respectively iron carbon filler, sulphur and zeolite, and volume ratio are as follows: iron carbon filler: sulphur: zeolite=1:1:2, composite filling account for
The 50% of reactor volume, wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, hydraulic detention time HRT=4h, dissolved oxygen DO=1.0- of intaking
Under conditions of 2.0mg/L, averagely water outlet nitrate is 2.6-3.2mg/L, and the removal rate of nitrate nitrogen is 89-91%, and
Accumulation without ammonia nitrogen and nitrite nitrogen, water outlet pH are 6.3-6.5.
Embodiment 5:
Low-carbon-source in embodiment 5 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper is respectively iron carbon filler, sulphur and haydite, and volume ratio are as follows: iron carbon filler: sulphur: haydite=1:1:2, composite filling account for
The 50% of reactor volume, wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 3.4-4.1mg/L, and the removal rate of nitrate nitrogen is 86-88%, and without ammonia
The accumulation of nitrogen and nitrite nitrogen, water outlet pH are 5.9-6.2.
Embodiment 6:
Low-carbon-source in embodiment 6 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper respectively iron carbon filler, sulphur, lime stone and zeolite, volume ratio are as follows: iron carbon filler: sulphur: lime stone: zeolite=1:
1:1:1, composite filling account for the 50% of reactor volume, and wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 2.1-3.1mg/L, and the removal rate of nitrate nitrogen is 89-93%, and without ammonia
The accumulation of nitrogen and nitrite nitrogen, water outlet pH are 6.9-7.1.
Embodiment 7:
Low-carbon-source in embodiment 7 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper respectively iron carbon filler, sulphur, oyster shell and medical stone, volume ratio are as follows: iron carbon filler: sulphur: lime stone: zeolite=
1:3:2:2, composite filling account for the 50% of reactor volume, and wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 1.4-2.1mg/L, and the removal rate of nitrate nitrogen is 93-95%, and without ammonia
The accumulation of nitrogen and nitrite nitrogen, water outlet pH are 6.1-6.7.
Embodiment 8:
Low-carbon-source in embodiment 8 adds the composite filling of efficient denitrification filter pool, in reactor composite filling from it is lower to
Upper respectively iron carbon filler, sulphur, oyster shell and medical stone, volume ratio are as follows: iron carbon filler: sulphur: lime stone: zeolite=
3:1:2:2, composite filling account for the 50% of reactor volume, and wherein the preparation method is the same as that of Example 1 for iron carbon filler.
By the static biofilm stage same as Example 1, after continuous cultivation stage and stable operation stage, it is average into
Water nitrate is 30 ± 5mg/L, C/N=1.5-2, intake dissolved oxygen DO=1.0-2.0mg/L, hydraulic detention time HRT
Under conditions of=4h, averagely water outlet nitrate is 3.8-5.1mg/L, and the removal rate of nitrate nitrogen is 83-87%, and without ammonia
The accumulation of nitrogen and nitrite nitrogen, water outlet pH are 7.3-8.1.
Comparative example 1
Experiment condition using volcanic rock conventional fillers and the experiment condition using composite filling of the present invention are complete
It is identical, the composite filling in reactor is only substituted for volcanic rock conventional fillers.
It is 30 ± 5mg/L in average water inlet nitrate, C/N=1.5-2, hydraulic detention time HRT=4h water inlet are molten
Under conditions of solving oxygen DO=1.0-2.0mg/L, volcanic rock conventional fillers and use are separately added into two identical reactors
Composite filling made from embodiment 1, volume shared by filler are the 50% of reactor volume, and sludge additional amount is to fill reactor
Standard, static biofilm stage same as Example 1 after continuous cultivation stage and stable operation stage, are routinely filled out using volcanic rock
Expect and uses the reactor removal effect of composite filling as shown in Figure 1.
When as seen from Figure 1, using volcanic rock conventional fillers, nitrate nitrogen removal efficiency is 40%, and is filled out using combination
Material, average removal rate can reach 92%.If the reactor using conventional fillers will obtain good removal effect, need with grape
Sugar is used as carbon source, C/N=6.4-7.5, much larger than carbon source needed for composite filling.
The use of the dominant bacteria in the reactor of volcanic rock conventional fillers is heterotrophic denitrifying Bacteria, but works as C/N=1.5-2
When, the living condition of heterotroph is bad, and it is incomplete to will cause denitrification process, generates nitrite nitrogen accumulation, while denitrification effect
Generally.
Comparative example 2
It is 30 ± 5mg/L, C/N=1.5-2, hydraulic detention time HRT=4h dissolved oxygen in average water inlet nitrate
Under conditions of concentration is 1.0-2.0mg/L, it is separately added into two identical reactors made from sulphur filler and embodiment 1
Composite filling, volume shared by filler are the 50% of reactor volume, and sludge additional amount, which is subject to, fills reactor, with embodiment 1
The identical static state biofilm stage after continuous cultivation stage and stable operation stage, uses sulphur filler and using composite filling
Reactor removal effect is as shown in Figure 2.
When as seen from Figure 2, using sulphur filler, average removal efficiency is 78%, and uses composite filling, is averagely gone
Except rate can reach 92%.Simple uses sulphur to will cause electron donor deficiency as filler, so that nitrous state occurs in water outlet
Nitrogen accumulation, while reactor assembly pH value can also be made to decline.
Note that above are only presently preferred embodiments of the present invention.It will be appreciated by those skilled in the art that the present invention is not limited to here
The specific embodiment is able to carry out for a person skilled in the art and various apparent change, readjusts, be combineding with each other
With substitution without departing from protection scope of the present invention.Therefore, although having been carried out more in detail by above embodiments to the present invention
Thin explanation, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, can also include
More other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (12)
1. a kind of denitrification filter pool composite filling, comprising: iron carbon filler, sulphur, porous material and pH padded coaming.
2. denitrification filter pool composite filling according to claim 1, wherein the iron carbon filler includes following component: also
Former iron powder, active carbon, copper powder, binder, pore creating material and pH adjusting agent.
3. denitrification filter pool composite filling according to claim 2, wherein the iron carbon filler each component mass ratio are as follows:
Reduced iron powder 40-45%, active carbon 12-15%, copper powder 8-10%, binder 20-25%, pore creating material 5-8% and pH are adjusted
Agent 5-8%.
4. denitrification filter pool composite filling according to claim 3, wherein the binder is selected from calcium sulfate, alginic acid
One of sodium, Arabic gum and polyvinyl alcohol are a variety of；
The pH adjusting agent is selected from one of sodium bicarbonate, sodium dihydrogen phosphate, sodium hydroxide and calcium carbonate or a variety of；
The pore creating material is selected from ammonium hydrogen carbonate.
5. denitrification filter pool composite filling according to any one of claim 2 to 4, wherein the grain of the reduced iron powder
Diameter is 150-200 mesh, and the partial size of the active carbon is 150-200 mesh, and the partial size of the copper powder is 150-200 mesh.
6. denitrification filter pool composite filling according to any one of claim 2 to 4, wherein the iron carbon filler is ball
Shape, diameter 9-12mm.
7. denitrification filter pool composite filling according to any one of claim 2 to 4, wherein the system of the iron carbon filler
Preparation Method the following steps are included:
(1) by the iron carbon filler feed components blending and mixing, be slowly added to material quality 15-20% water be mixed to form it is viscous
Thick shape mixture；
(2) mixture obtained in step (1) is filled into mold, 45-60 DEG C in a vacuum drying oven, dry 6-8h；
(3) the product high-temperature roasting under inert atmosphere gases that will be obtained after vacuum drying in step (2), that is, be made iron carbon and fill out
Material.
8. denitrification filter pool composite filling according to claim 7, wherein the inert atmosphere gases are selected from inert gas
Or one of nitrogen or a variety of；
The condition of the high-temperature roasting is to roast 2-4h at 400-700 DEG C.
9. denitrification filter pool composite filling according to any one of claim 1 to 4, wherein the porous material is selected from
One or more of medical stone, zeolite, haydite and volcanic rock；The pH padded coaming is selected from oyster shell and lime
One or both of stone.
10. denitrification filter pool composite filling according to any one of claim 1 to 4, wherein the group of the composite filling
Conjunction sequence is respectively iron carbon filler, sulphur, pH padded coaming and porous material from top to bottom；
The iron carbon filler, sulphur, pH padded coaming and porous material volume ratio be 1-3:1-3:0-2:1-2.
11. denitrification filter pool composite filling according to any one of claim 1 to 4, wherein the grain of the porous material
Diameter is 3-5mm；The partial size of the pH padded coaming is 3-5mm；The partial size of the sulphur is 0.5-1mm.
12. denitrification filter pool composite filling described in a kind of any one of claims 1 to 11 handle nitrogenous sanitary sewage and
Application in the anaerobic reactor of industrial wastewater, wherein the composite filling is filled in anaerobic reactor, and packed height is to detest
The 50-80% of oxygen reactor height.
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