CN109761347A - Based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe and device - Google Patents
Based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe and device Download PDFInfo
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Abstract
The invention discloses one kind to be based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe and device, this method comprises the following steps: 1) gas transfer membrane module, and the filling-modified gel biological carbon filling material around gas transfer membrane module being arranged in sewage water denitrification device；The modified gel biology carbon filling material is obtained by charcoal through gelatinous mass fixation；2) sewage containing nitrate nitrogen is introduced into sewage water denitrification device；3) to being passed through the gas organic matter that can be used as the electron donor of anti-nitration reaction on the inside of gas transfer membrane module；4) denitrifying bacteria carries out anti-nitration reaction using the nitrate nitrogen and gas organic matter of gas transfer membrane module interface two sides, is nitrogen by the nitrate-nitrogen reduction in sewage.The device includes device noumenon, and gas transfer membrane module is arranged inside, and the filling-modified gel biological carbon filling material around gas transfer membrane module.The present invention has nitric efficiency high, reduces the discharge of greenhouse gases, operation require it is low, run it is relatively stable, it is convenient for management the advantages that.
Description
Technical field
The invention belongs to sewage treatment fields, in particular to one kind to be based on the denitrifying sewage plant tailwater depth of anaerobe
Spend denitrogenation method and device.
Background technique
Nitrogen is present in water body in the form of organic nitrogen and two kinds of inorganic nitrogen, and organic nitrogen turns after microorganism decomposition in water body
Turn to inorganic nitrogen, and inorganic nitrogen is mainly based on nitrate nitrogen (including NO3-, NO2-).
China is as large agricultural country, and chemical fertilizer is largely come into operation, thus nitrate nitrogen is widely present in underground water and ground
In table water, water eutrophication phenomenon is caused, is proliferated algae largely, cause water hypoxia, causes water quality deterioration, it is final broken
The ecological balance of bad water environment.In addition, high concentration nitrate is easy to react with blood of human body, human health is threatened.
Meanwhile the raising again and again of sewage drainage standard, especially surface water Group III standard requirements TN≤1mg/L, give advanced nitrogen technology
Propose very big challenge.
Currently used nitrate nitrogen denitrogenation means are anaerobe denitrification technologies, utilize and are largely present at sewage
Denitrifying bacteria in reason system utilizes NO under conditions of free-dioxygen2 -And NO3 -In N+5 and N+3 as energetic supersession
In electron acceptor, O2H is generated as hydrogen acceptor2O and OH-Basicity, organic matter provide energy as carbon source and electron donor and obtain
To oxidation-stabilized.Specific mechanism in relation to anti-nitration reaction is detailed in https: //wenku.***.com/view/e606c80e
571252d380eb6294dd88d0d232d43c02.html。
Methane is a kind of renewable energy that nature is widely present and a kind of strong greenhouse gas, the greenhouse caused
Effect is CO221 times, have tremendous influence to global warming.It is mainly derived from detesting in municipal sewage treatment and garbage loading embeading
Aerobe fermentation process, wetland, ocean, soil etc. also have a large amount of methane and generate in nature.Experimental results demonstrate methane can fill
Enough energy are provided when the electron donor of anti-nitration reaction, while for the growth of denitrifying bacteria.It is supplied with other organic electronics
Body is compared, and methane has the characteristics that efficient, small toxicity, can be consumed methane again under the premise of product harmless and be alleviated greenhouse effect
It answers.
But methane indissoluble in water, so that denitrifying bacteria utilization efficiency is very low.Using other gas organic matters such as ethane
As electron donor, there is also identical technical problems.With countries in the world constantly mentioning to sewage disposal plant effluent water standard
Height requires also to be increasingly stringenter to the denitrogenation of sewage, and existing denitrogenation means have been unable to satisfy effluent quality requirement.
Summary of the invention
It is high based on the denitrifying sewage plant tail water of anaerobe that the purpose of the present invention is to provide a kind of nitric efficiencies
Deep denitrification method and device.
To achieve the above object, provided by the present invention to be based on the denitrifying sewage plant Tailwater Depth denitrogenation of anaerobe
Method includes the following steps:
1) gas transfer membrane module is set in sewage water denitrification device, and filling-modified around gas transfer membrane module
Gel biological carbon filling material；The modified gel biology carbon filling material is obtained by charcoal through gelatinous mass fixation；
2) sewage containing nitrate nitrogen is introduced into sewage water denitrification device, contained in sewage or added with denitrification can be carried out
The denitrifying bacteria of reaction, denitrifying bacteria are attached on gas transfer membrane module outer surface after entering sewage water denitrification device；
3) to being passed through the gas organic matter that can be used as the electron donor of anti-nitration reaction on the inside of gas transfer membrane module；
4) denitrifying bacteria for being attached to gas transfer membrane module outer surface utilizes the nitrate nitrogen and gas of interface two sides
Organic matter carries out anti-nitration reaction, is nitrogen by the nitrate-nitrogen reduction in sewage.
Preferably, the preparation of the modified gel biology carbon filling material includes the following steps:
1.1) biological powdered carbon is prepared by biomass；
1.2) biological powdered carbon is impregnated in the gel suspension containing gelatinous mass, keeps the two sufficiently mixed using ultrasonic treatment
It closes；
1.3) precipitating is collected by filtration, gained precipitating is dried to get granular modified gel biology carbon filling material is arrived.
Preferably, in the step 1.1), the preparation process of biological powdered carbon is as follows: using biomass as raw material, 200~
It is pyrolyzed 1~6h at 800 DEG C, obtained charcoal is subjected to dedusting, ball-milling treatment is then carried out, obtains partial size 400~1000
Mesh biological powdered carbon (excessively corresponding mesh number standard screen) below.Ball-milling treatment can increase charcoal specific surface area and porosity, improve
Adsorption capacity is conducive to subsequent denitrogenation processing.
Preferably, the biomass is the combination of one or more of levant cotton exocarp, broomcorn millet chaff, stalk, rice husk；The jello
Matter is carragheen or sodium alginate；The granularity of the modified gel biology carbon filling material is in 50~80mm.
Preferably, in the step 4), portion gas organic matter, which passes through gas transfer membrane module, to be dispersed and enters in sewage,
Into in the microcellular structure of modified gel biology carbon filling material；Part denitrifying bacteria is attached on modified gel biology carbon filling material,
Anti-nitration reaction is carried out using neighbouring gas organic matter and nitrate nitrogen, is nitrogen by the nitrate-nitrogen reduction in sewage.
Preferably, the gas organic matter is methane.It, on the one hand can be with using methane as anti-nitration reaction electron donor
Directly using output methane a large amount of during sewage treatment, garbage loading embeading, sewage treatment plant does not need to buy methane from outside, because
And it can substantially save the cost；On the other hand, methane is a kind of greenhouse gases, is reacted as electron donor and NO3-, product will not
It causes damages to environment, alleviates greenhouse effects while reducing nitrate nitrogen content in water.
Invention also provides it is a kind of for realize preceding method and design based on the denitrifying sewage of anaerobe
Plant tail water deep denitrogenation device, including device noumenon, described device ontology are the container of integral sealing, are provided in the container
Gas transfer membrane module, and the filling-modified gel biological carbon filling material around gas transfer membrane module, on described device ontology
It is provided with the sewage inlet for inputting the sewage containing nitrate nitrogen, the treated water outlet for exporting the water after denitrogenation and is used for
The gas discharge outlet of the gas generated in anti-nitration reaction is discharged, is provided on the gas transfer membrane module for inputting anti-nitre
The air feed interface for changing reaction electron donor, be provided on described device ontology for outer gas tube and the air feed interface into
The installing port of row connection.
Preferably, the top of the container is provided with three-phase distributor, and with the outlet of its water phase for the treated water outlet,
With its gaseous phase outlet for the gas discharge outlet.When the mixed liquor of gas, liquid, solid rises in three phase separator, three phase separator
Gas that reaction generates, treated water can be separated with modified gel biology carbon filling material, the gas after separation is through gas
The discharge of body outlet, the purified water out discharge of water after separation.
Preferably, the gas transfer membrane module is made of hollow-fibre membrane.There are many membrane module forms, mainly there is plate
Film, rolled film, hollow-fibre membrane etc., in recent years extensive concern of the research of hollow-fibre membrane by academia and industry.This
Scheme uses hollow-fibre membrane, and compared with other films, hollow-fibre membrane has the advantage that the film surface of 1) unit volume membrane module
Product is bigger, and membrane module loading density with higher increases the mass-transfer performance of gas；2) structure of hollow-fibre membrane has good
Self-supporting effect；3) membrane module is easily prepared.
Preferably, the material of the hollow-fibre membrane is Polyimide Hollow Fiber.Polyimides is a kind of heat resistance
Energy is good, mechanical performance is excellent, stable chemical performance high-performance polymer material, has excellent gas transfer performance.
Preferably, the quantity of the gas transfer membrane module is one, is vertically set on device noumenon middle position；Or
Person, the quantity of the gas transfer membrane module be it is multiple, vertical and scattering device is in device noumenon.
Compared with prior art, the beneficial effects of the present invention are:
1) denitrifying bacteria is attached on gas transfer membrane module, and the electronics that transmitting comes on the inside of film can directly be utilized to supply
Body is reacted with the nitrate nitrogen in sewage on the outside of mould, and solving the gas electronics such as methane donor, solubility is low in water, reacts
The low problem of utilization rate.
2) charcoal that modified gel biology carbon filling material uses biomass to fire for raw material is raw material, and charcoal is a kind of collection
The environment-friendly materials of inexpensive, multi-functional, advantages of environment protection, have been widely used for reduction of greenhouse gas discharge, heavy metal
With the fields such as the environment remediation of organic pollutant, but often catalytic activity is insufficient and is difficult to recycle for free charcoal, to limit
Its application is made.Charcoal is fixed in the present invention, i.e., becomes gel after modified, improves urging for charcoal
The property changed and reuse efficiency, further enhance the denitrification effect of device, play synergistic effect.
3) present invention increases modified gel biology carbon filling material, enhances denitrogenation on the basis of existing denitrification technology
Ability makes TN index in water outlet reach IV class of surface water~Group III water body standard, has nitric efficiency high, operates and requires low, fortune
The advantages that row is relatively stable, convenient for management.
4) present invention is generally directed to nitrate nitrogen (NO3 -、NO2 -) be designed, but due to organic nitrogen, ammoniacal nitrogen (NH3, NH4 +)
Nitrate nitrogen can be converted into via the prior art, therefore present invention combination dependent conversion technique also may be implemented to organic nitrogen, ammonia state
The processing of nitrogen.
Detailed description of the invention
Fig. 1 is the structure based on the denitrifying sewage plant Tailwater Depth nitrogen rejection facility of anaerobe designed by the present invention
Schematic diagram in figure in addition to sewage water denitrification device itself, while depicting the external structures such as pump and gas tank to show its workflow
With connection.
Wherein: device noumenon 1, gas transfer membrane module 2, modified gel biology carbon filling material 3, sewage inlet 4, air feed interface
5, treated water outlet 6, gas discharge outlet 7, three-phase distributor 8, upstream sewage-treatment plant 9, pump 10, gas tank 11, flowmeter 12
Specific embodiment
The following further describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
As shown in Figure 1, based on the denitrifying sewage plant Tailwater Depth nitrogen rejection facility of anaerobe designed by the present invention,
Including device noumenon 1, device noumenon 1 is the container (except inlet and outlet) of integral sealing, builds anaerobic environment, makes denitrifying bacteria
Anti-nitration reaction occurs, achievees the purpose that denitrogenation.
Gas transfer membrane module 2 is vertically installed at the interior central position of device noumenon 1, gas transfer membrane module 2
Upper end is not open, and lower end is provided with air feed interface 5.Have many advantages, such as that mass-transfer performance is excellent in view of Polyimide Hollow Fiber,
Gas transfer membrane module 2 is all made of multi beam Polyimide Hollow Fiber composition in various embodiments of the present invention.Gas transfer film group
Modified gel biology carbon filling material 3 is filled with around part 2.
The top of device noumenon 1 is provided with treated water outlet 6 and gas discharge outlet 7, and lower part is provided with sewage inlet 4, bottom
Portion is provided with the installing port being attached for outer gas tube and air feed interface 5.
Sewage containing nitrate nitrogen from upstream sewage-treatment plant 9 is transported in device noumenon 1 by pump 10, and water level maintains
In gas transfer membrane module 2 and 3 or more modified gel biology carbon filling material.
Air feed interface 5 is pierced by from installing port, is connected by hose with the gas tank 11 for being equipped with flowmeter 12, is equipped in gas tank 11
As the methane of electron donor, methane can be passed directly in gas transfer membrane module 2 by hose, and flowmeter 12 can be to it
Flow velocity is controlled.
The top of device noumenon 1 is provided with three-phase distributor 8, and water phase outlet is treated water outlet 6, gaseous phase outlet
As gas discharge outlet 7.
Invention also provides the methods that the above-mentioned sewage water denitrification device of application carries out sewage water denitrification processing comprising as follows
Step:
1) modified gel biology carbon filling material 3 is prepared, and is filled in device noumenon 1 around gas transfer membrane module 2, is filled
Afterwards as shown in Fig. 1；
The preparation step of modified gel biology carbon filling material 3 is as follows:
1.1) it prepares biological powdered carbon: being with biomass (combination of one or more of levant cotton exocarp, broomcorn millet chaff, stalk, rice husk)
Raw material, is pyrolyzed 1~6h at 200~800 DEG C, then the charcoal dedusting that will be obtained carries out ball-milling treatment, obtains partial size and exist
400~1000 mesh biological powdered carbon below；
1.2) biological powdered carbon is impregnated in the gel suspension of carragheen or sodium alginate, fills the two using ultrasonic treatment
Divide mixing；
1.3) precipitating is collected by filtration, gained precipitating is dried raw to get the modified gel to diameter in 50~80mm
Object carbon filling material 3.
2) sewage containing nitrate nitrogen is introduced into sewage water denitrification device, the anti-of anti-nitration reaction can be carried out by containing in sewage
Nitrobacteria, denitrifying bacteria are attached on 2 outer surface of gas transfer membrane module after entering sewage water denitrification device；
3) the gas organic matter that can be used as the electron donor of anti-nitration reaction is passed through to the inside of gas transfer membrane module 2；
Since methane has the advantages such as at low cost, electron donor of the methane as anti-nitration reaction is all made of in various embodiments of the present invention.
4) denitrifying bacteria for being attached to 2 outer surface of gas transfer membrane module utilizes the nitrate nitrogen and gas of interface two sides
Organic matter carries out anti-nitration reaction, is nitrogen by the nitrate-nitrogen reduction in sewage；Meanwhile portion gas organic matter is passed across gas
Plasma membrane component 2 disperses and enters in sewage, into the microcellular structure of modified gel biology carbon filling material；Denitrifying bacteria is attached for part
On modified gel biology carbon filling material 3, carry out anti-nitration reaction using neighbouring gas organic matter and nitrate nitrogen, will be in sewage
Nitrate-nitrogen reduction be nitrogen.
The above method is described further below by way of comparative example and embodiment.
Comparative example 1
Experimental water is from Wuhan City's sewage plant tail water, index before testing are as follows: COD 39mg/L, TN 14.7mg/
L, PH 7.5.
The dischargeable capacity 4.5L of device noumenon 1 in this comparative example, is inside not filled with modified gel biology carbon filling material 3.
The experimental procedure of this comparative example are as follows: methane gas is passed into gas transfer membrane module 2, tail water is passed into device
It (is intake using continuous flow) in ontology 1, intake flow velocity 3ml/min, hydraulic detention time 150min.Methane gas is through gas transfer
2 mass transfer of membrane module, with NO in sewage3 -Reaction, the gas generated after reaction, processing water are separated through three phase separator, after separation
Gas is discharged through gas discharge outlet 7, and the purified water out 6 of the water after separation is discharged.
Assay, effluent index are as follows: COD 34mg/L, TN 4.03mg/L, removal rate reach are carried out to water outlet
72.6%, it can only achieve surface water level-one A discharge into water standard.
Embodiment 1
Experimental water is from Wuhan City's sewage plant tail water, index before testing are as follows: COD 39mg/L, TN 14.7mg/
L, PH 7.5.The standard method that analysis method employed in test is issued according to State Bueau of Environmental Protection.
Experimental procedure is using levant cotton exocarp as biomass, and 400 DEG C of pyrolysis 2h, obtained charcoal is gone in Muffle furnace
Then ash is impregnated in carragheen (or sodium alginate) gel suspension, being put in ultrasound is sufficiently mixed the two as gel life
Object charcoal obtains the modified gel biology carbon filling material 3 that diameter is 60mm, is launched in device noumenon 1.
Methane gas is passed into gas transfer membrane module 2, biochemistry pool water outlet is passed into device noumenon 1 (using continuous
Flow into water), methane gas is through 2 mass transfer of gas transfer membrane module, with NO in sewage3 -Reaction, after reaction sewage further with modification
Gel biological carbon filling material 3 acts on, and the gas of generation, gel biological charcoal, processing water three separate through three phase separator, after separation
Gas is discharged through gas discharge outlet 7, and gel biological charcoal slowly settles back reaction zone, and the purified water out 6 of the water after separation is discharged.
Assay, effluent index are as follows: removal rate after COD 27mg/L, TN 1.98mg/L, 120min are carried out to water outlet
Up to 86.5%, reach IV class discharge into water standard of surface water.
Compared with comparative example 1, after the present embodiment increases modified gel biologic packing material in device noumenon 1, denitrification effect is obvious
Enhancing, and rate is accelerated, hydraulic detention time is short, can reduce 1 dischargeable capacity of device noumenon, reduce cost.
Embodiment 2
Experimental water is from Wuhan City's sewage plant tail water, index before testing are as follows: COD 39mg/L, TN 14.7mg/
L, PH 7.5.The standard method that analysis method employed in test is issued according to State Bueau of Environmental Protection.
Experimental procedure increases this work of ball milling with embodiment 1, only after charcoal dedusting.
Assay, effluent index are as follows: removal rate after COD 24mg/L, TN 0.76mg/L, 90min are carried out to water outlet
Up to 94.8%, meet III class discharge into water standard of surface water.
Compared with embodiment 1, the present embodiment TN removal rate and rate increase, the reason is that charcoal compares table after ball milling
Area increases, and hole increases, adsorption capacity enhancing, while the increase of specific surface area is conducive to the load of denitrifying bacteria, strengthens
Treatment effect.
Claims (10)
1. one kind is based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe, it is characterised in that:
Include the following steps:
1) gas transfer membrane module (2) are set in sewage water denitrification device, and fill and changes around gas transfer membrane module (2)
Property gel biological carbon filling material (3)；The modified gel biology carbon filling material (3) is obtained by charcoal through gelatinous mass fixation；
2) sewage containing nitrate nitrogen is introduced into sewage water denitrification device, contained in sewage or added with anti-nitration reaction can be carried out
Denitrifying bacteria, denitrifying bacteria is attached on the outer surface of gas transfer membrane module (2) after entering sewage water denitrification device；
3) to being passed through the gas organic matter that can be used as the electron donor of anti-nitration reaction on the inside of gas transfer membrane module (2)；
4) denitrifying bacteria for being attached to gas transfer membrane module (2) outer surface has using the nitrate nitrogen and gas of interface two sides
Machine object carries out anti-nitration reaction, is nitrogen by the nitrate-nitrogen reduction in sewage.
2. according to claim 1 be based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe, feature
It is:
The preparation of the modified gel biology carbon filling material (3) includes the following steps:
1.1) biological powdered carbon is prepared by biomass；
1.2) biological powdered carbon is impregnated in the gel suspension containing gelatinous mass, is sufficiently mixed the two using ultrasonic treatment；
1.3) precipitating is collected by filtration, gained precipitating is dried to get granular modified gel biology carbon filling material (3) is arrived.
3. according to claim 2 be based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe, feature
Be: in the step 1.1), the preparation process of biological powdered carbon is as follows: using biomass as raw material, being pyrolyzed 1 at 200~800 DEG C
Obtained charcoal is carried out dedusting, then carries out ball-milling treatment, obtain partial size in 400~1000 mesh biology below by~6h
Powdered carbon.
4. according to claim 2 be based on the denitrifying sewage plant Tailwater Depth denitrogenation method of anaerobe, feature
Be: the biomass is the combination of one or more of levant cotton exocarp, broomcorn millet chaff, stalk, rice husk；The gelatinous mass is carragheen
Or sodium alginate；The granularity of the modified gel biology carbon filling material (3) is in 50~80mm.
5. according to any one of claims 1 to 4 be based on the denitrifying sewage plant Tailwater Depth denitrogenation of anaerobe
Method, it is characterised in that: in the step 4), portion gas organic matter, which passes through gas transfer membrane module (2), to be dispersed and enter dirty
In water, into the microcellular structure of modified gel biology carbon filling material；Part denitrifying bacteria is attached to modified gel charcoal and fills out
Expect on (3), carries out anti-nitration reaction using neighbouring gas organic matter and nitrate nitrogen, be nitrogen by the nitrate-nitrogen reduction in sewage
Gas.
6. according to any one of claims 1 to 4 be based on the denitrifying sewage plant Tailwater Depth denitrogenation of anaerobe
Method, it is characterised in that: the gas organic matter is methane.
7. it is a kind of aim at sewage denitrification method described in any one of claim 1~6 and design based on the anti-nitre of anaerobe
The sewage plant Tailwater Depth nitrogen rejection facility of change, it is characterised in that: including device noumenon (1), described device ontology (1) is whole close
The container of envelope is provided with gas transfer membrane module (2) in the container, and fills and change around gas transfer membrane module (2)
Property gel biological carbon filling material (3), be provided on described device ontology (1) sewage inlet (4) for inputting the sewage containing nitrate nitrogen,
Gas row for exporting the treated water outlet (6) of the water after denitrogenation and for the gas generated in anti-nitration reaction to be discharged
It exports (7), the air feed interface (5) for inputting anti-nitration reaction electron donor is provided on the gas transfer membrane module (2),
The installing port being attached for outer gas tube and the air feed interface (5) is provided on described device ontology (1).
8. according to claim 7 be based on the denitrifying sewage plant Tailwater Depth nitrogen rejection facility of anaerobe, feature
Be: the top of the container is provided with three-phase distributor (8), and with the outlet of its water phase for the treated water outlet (6), with it
Gaseous phase outlet is the gas discharge outlet (7).
9. according to claim 7 or 8 be based on the denitrifying sewage plant Tailwater Depth nitrogen rejection facility of anaerobe, spy
Sign is: the gas transfer membrane module (2) is made of hollow-fibre membrane.
10. according to claim 7 or 8 be based on the denitrifying sewage plant Tailwater Depth nitrogen rejection facility of anaerobe,
Be characterized in that: the quantity of the gas transfer membrane module (2) is one, is vertically set on device noumenon (1) middle position；Or
Person, the quantity of the gas transfer membrane module (2) be it is multiple, vertical and scattering device is in device noumenon (1).
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| CN112707462A (en) * | 2020-12-03 | 2021-04-27 | 南京大学 | Sequential adsorption treatment method for toxicity reduction of organic nitrogen industrial biochemical tail water |
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Application publication date: 20190517 |
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