CN110127872A - A kind of micro-nano bubble releasable material and preparation method thereof for natural water body reparation - Google Patents
A kind of micro-nano bubble releasable material and preparation method thereof for natural water body reparation Download PDFInfo
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- CN110127872A CN110127872A CN201910418543.8A CN201910418543A CN110127872A CN 110127872 A CN110127872 A CN 110127872A CN 201910418543 A CN201910418543 A CN 201910418543A CN 110127872 A CN110127872 A CN 110127872A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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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
- C02F1/00—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
- C02F7/00—Aeration of stretches of water
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to micro-nano bubble technologies of preparing and Water Environmental Pollution Control field, a kind of micro-nano bubble releasable material and preparation method thereof for natural water body reparation is disclosed, after the material is invested in target water body, material can form a large amount of micro-nano bubble in water, wherein body phase micro-nano bubble is scattered in overlying water, the efficient fast oxygenation of overlying water can be achieved, and interface micro-nano bubble is present in coating due to being attached to material interface, it is directly contacted with anoxic sediments object, can it is long-acting reverse water/sediment interface oxidation-reduction potential, it is passivated surface deposit.And the release performance of micro-nano bubble can be regulated and controled by controlling the property of material.The method has both the ecological security and long-term effect of natural water body improvement, it is nontoxic without using chemical reagent, it can efficiently eliminate natural water body anoxic and black and odorous water phenomenon, accelerate the oxygenolysis of reducing substances in overlying water, is that good condition is built in the restoration of the ecosystem of polluted-water.
Description
Technical field
The micro-nano bubble releasable material and preparation method thereof that the present invention relates to a kind of for natural water body reparation, belongs to micro-nano
Bubble technology of preparing and Water Environmental Pollution Control field.
Background technique
Dissolved oxygen (DO) is environmental factor important in aquatic ecosystem, is maintaining aquatic life activity and aquatic ecosystem
The Functions such as self-cleaning irreplaceable role.It is got worse however as eutrophications such as river, lakes, You Haizao
China takes place frequently, and is deposited to deposit surface after degradable frustule is dead, rots and decomposition causes overlying water DO concentration
Rapid decline, cause water hypoxia phenomenon, this not only severe exacerbation water quality, organism in water group and Sediments
Quality also destroys the balance and capacity of self-regulation of the ecosystem, causes the degeneration of function of water body.In addition, having not enough time to drop
The organic matter of solution transfers to continue to degrade under anaerobic, generates the sulfide compound of reproducibility and the H of small molecule2S、NH3Etc. smelly
The black indissoluble substance such as taste substance and FeS and MnS, causes usually said black and odorous water phenomenon.Algal tufa outburst season, by
Black smelly phenomenon caused by water body and deposit anoxic generally occurs in the important lake in China such as Taihu Lake, Chaohu and Dian Chi etc..
There are three types of the common technical measures for being directed to water body and deposit oxygen deficit problem.The first is aeration oxygen replenishing technology,
Aeration can effectively promote the DO of water body, but there are the power of great number and operating costs for this method, and having causes deposit to hang again
Floating, bottom water body heating and water body go stratification etc. to may cause the risk that technology implements failure；Second is deposit nitric acid
Calcium injection technique, the mechanism of action are that nitrate ion is the electron acceptor that oxidisability is only second to oxygen, deposition equally can be improved
The oxidation-reduction potential of object, while calcium ion forms slightly solubility " calcium phosphorus " in combination with the phosphate radical in deposit, sinks to reduce
The endogenous polyamine of product object, but the technology will increase the concentration of water body nitrate nitrogen and have the risk of eco-toxicity；The third is with mistake
Calcium oxide (magnesium) solid oxygen release agent soverlay technique as main component, oxygen release agent generate corresponding alkali and oxygen after reacting with water,
And then oxygenation is carried out to water and deposit surface, although most of oxygen release agent reduces calper calcium peroxide all in the form of cladding
The reaction rate of (magnesium) and water increases its action time, but its raising that inevitably will cause surrounding water pH, Er Qieshi
It is more to generate oxygen, corresponding generation alkaline matter is also more.These three technologies are all difficult to because there is technological deficiency on a large scale
Applied to actual anoxic water remediation.Therefore need development it is new can efficiently to promote water body DO horizontal but also improve deposit
Anaerobic environment, and have both the low-cost technologies of ecological security and environment friendly, the water body that Lai Gaishan is got worse simultaneously
With deposit anoxia phenomenon.
Summary of the invention
The present invention is directed to by the micro-nano bubble with high mass transfer efficiency, high activity and overlength stability, solve it is current because
Eutrophication and water body caused by the algal tufa that increasingly frequently breaks out and deposit oxygen deficit problem lack economic, long-acting solution
Problem provides the micro-nano bubble that can be used to repair natural water body that production method is simple, material source is extensive, environmental-friendly
Releasable material, which can act on overlying water and water/sediment interface simultaneously, and is effectively isolated by oxygen-containing coating
Reducing substances in deposit.Specifically, micro-nano bubble is generated in water after material is applied to target water body,
Wherein the efficient fast oxygenation, it can be achieved that overlying water is distributed in overlying water after the release of body phase micro-nano bubble, and interface is micro-
Bubble of receiving then is fixed by the surface of material, is formed and is stablized lasting oxygen-containing coating, to reverse the oxidation of water/sediment interface
Reduction potential is formed simultaneously the oxidization isolation layer of deposit, prevents reductive pollutants from discharging to overlying water.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that natural subsidence can be passed through
Body phase and interface micro-nano bubble are transported to deposit surface by mode.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that material therefor is porosity material
Material can be the active carbon that processing is formed, be also possible to clay or mineral, such as zeolite, local soil, pelelith, diatomite, swollen
Moisten the one or more of soil, kaolin, concave convex rod, sepiolite, montmorillonite etc..
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that control material can be passed through
Hydrophilic and hydrophobic regulates and controls the quantity, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles of micro-nano bubble.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that can be by controlling material table
The size and concentration of face regulate and control the quantity of micro-nano bubble, size, the release time of body phase bubble and interfacial bubbles
Fixed efficiency.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that control material can be passed through
Specific surface area regulates and controls the quantity, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles of micro-nano bubble.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that control material can be passed through
Particle size regulates and controls the quantity, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles of micro-nano bubble.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that the gas source of micro-nano bubble can be with
It is the gas that oxygen, ozone, air etc. contain a certain amount of oxygen.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that can be by the side that vacuumizes
Formula desorption falls the initial gas of material surface, and loads to object gas in porous material by way of High Pressure Absorption.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that can be inhaled by control high pressure
The pressure of attached process regulates and controls the production quantity of micro-nano bubble.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that material is before supporting gas
Will by high temperature, vacuumize or the modes such as high-temperature vacuum sufficiently remove moisture in material.
The micro-nano bubble releasable material for natural water body reparation, which is characterized in that material is before application again from true
It is taken out in empty pressure-swing absorption apparatus, exists side by side and use.
Micro-nano bubble releasable material preparation flow provided by the invention is simple, easy to use, implement general plan is low, motor-driven spirit
It is living, feasibility is high, generalization is strong, have no toxic side effect, oxygenation effect is obvious, be micro-nano bubble one in the application of restoration of the ecosystem field
It is secondary courageously and successfully attempt, expanded the application field of micro-nano bubble, can be not only used for lake, reservoir etc. anoxic water body or
The reparation of the black and odorous water of severe depletion of oxygen, it can also be used to which contaminated underground water body and the deep water water body with thermally stratified layer are repaired
Multiple, the DO level of improvement anoxic water body that can be steady in a long-term and the oxidation-reduction potential (ORP) of water/sediment interface improve water
The self-purification capacity of body facilitates the restoration of the ecosystem of polluted water body.Porous material used in this preparation method is from a wealth of sources, selects model
Enclose relatively wide, especially rich reserves and cheap natural minerals, it is environmental-friendly, it is without secondary pollution, can large-scale application in
Practical water remediation.
Detailed description of the invention
Fig. 1 is the NanoSight real-time detection figure of nano bubble.
Fig. 2 is the grain size distribution of nano bubble.
Fig. 3 is the micron bubble of diatomite release.
Fig. 4 is that 2cm mixing material oxygen carrier is covered to influence (1cm granular activated carbon and the 1cm for simulating column overlying water DO concentration
Natural zeolite).
Fig. 5 is influence of the 5cm granular activated carbon oxygen carrier covering to simulation column water/sediment interface ORP.
Fig. 6 is the schematic diagram that micro-nano bubble releasable material repairs natural water body.
Specific embodiment
Technology of the present invention and application are further described in detail below by embodiment.
The oxygen micro-nano bubble release performance of 1 natural zeolite of embodiment
Natural clinoptilolite is sieved after grinding, and takes the particle of 2-4mm, and deionized water sufficiently washs and washes powdery granule
Out, overnight, calcination 4h, cooling are stand-by at 350 DEG C in Muffle furnace after taking-up for 80 DEG C of drying after leaching water.It takes a certain amount of through washing
Wash and abundant dewatered zeolite sample be placed in independent intake valve and exhaust valve and resistance to certain high pressure and vacuum degree it is closed
In stainless steel equipment, Vacuum Pressure Swing Adsorption is carried out, vacuum condition is set as -0.09MPa 2h, O2High Pressure Absorption condition is
0.45MPa 0.5h, circulating vacuum transformation operating procedure 3 times, and the last time high-pressure balancing time is no less than 12h.Material decompression
Afterwards, investment is filled in the Organic glass column (internal diameter 64mm, high 17cm, effective volume about 0.5L) of oxygen saturation deionized water immediately,
Its time for discharging oxygen micro-nano bubble is more than 2d, and oxygen evolution amount is more than 3.6mg/g.
The particle diameter distribution of the oxygen nano bubble of 2 natural zeolite of embodiment release
Natural clinoptilolite is sieved after grinding, and takes the particle of 0.35-0.60mm, and deionized water sufficiently washs and will be powdered
Particle washes out, and overnight, calcination 4h, cooling are stand-by at 350 DEG C in Muffle furnace after taking-up for 80 DEG C of drying after leaching water.It takes certain
Washed and abundant dewatered zeolite sample is measured to be placed in independent intake valve and exhaust valve and resistance to certain high pressure and vacuum degree
Closed stainless steel equipment in, carry out Vacuum Pressure Swing Adsorption, vacuum condition is set as -0.09MPa 2h, O2High Pressure Absorption condition
It is 0.15MPa 0.5h, circulating vacuum transformation operating procedure 3 times, and the last time high-pressure balancing time is no less than 12h.Material drop
After pressure, investment stands for 24 hours equipped in the beaker of ultrapure water, the solution at intermediate position is taken, with NanoSight nano particle immediately
The oxygen nano bubble (NBs) that analyzer is discharged into overlying water to zeolite detects, and instrument parameter Camera level is 14,
Threshold is 4, the particle diameter distribution and real-time detection the result is shown in Figure 1 and Fig. 2 of nano bubble.
The air micron bubble form of 3 diatomite ore composition granule of embodiment release
Natural minerals diatomite is sieved after grinding, and takes the particle of 0.355-0.425mm, and deionized water sufficiently washs and by powder
Last shape particle washes out, and 80 DEG C of drying overnight, handle 12h in 90 DEG C of vacuum oven after leaching water after taking-up, and pressure is less than-
0.095MPa cools down spare.It takes a certain amount of diatomite particle handled well to be placed in glass slide, is dripped with rubber head dropper ultrapure
Water is flooded, and discharges the process of micron bubble with inverted microscope observation diatomite, and shoot the micron bubble of its release
Photo (Fig. 3).
4 oxygen micro-nano bubble of embodiment discharges granular activated carbon and natural zeolite mixing covering simulates column overlying water DO to Taihu Lake
Influence
It takes cocoanut active charcoal (2-5mm), deionized water sufficiently washs and washes out powdered active carbon, in 80 after bleeding water
DEG C drying 48h, by simulation column dimension weigh up covering 1cm active carbon needed for quality；At the same time, natural clinoptilolite (2- is taken
4mm), deionization sufficiently washs and washes out powdery granule, leach water after 80 DEG C drying overnight, after taking-up in Muffle furnace
At 350 DEG C after calcination 4h, cooling is stand-by, quality needed for equally weighing up simulation column dimension 1cm；Active carbon and natural zeolite are mixed
After conjunction, thin layer is placed in in independent intake valve and exhaust valve and the closed stainless steel equipment of resistance to certain high pressure and vacuum degree, into
Row Vacuum Pressure Swing Adsorption, vacuum condition are set as -0.09MPa 2h, O2High Pressure Absorption condition is 0.15MPa 0.5h, and circulation is true
Space-variant press operation step 3 time, and the last time high-pressure balancing time is no less than 12h.Deposit and lake water are derived from Jiangsu Province Taihu Lake
The area that the gulf Mei Liang algal tufa often accumulates is transferred into laboratory and fills column after deploying uniformly, pillar long 1m, internal diameter 64mm,
The high 10cm of deposit, overlying water depth 85cm.Pillar is covered after stable 10d at room temperature after installing.Micro-nano bubble discharges material
Material is depressured again before application, and immediately as a result uniform fold is shown in Fig. 4 in Taihu Lake simulation column after taking-up.As seen from the figure, 2cm thickness
Active carbon and zeolite mixing covering can the larger dissolved oxygen levels for promoting overlying water, and in 1d by it from 2mg/L or so
6mg/L or more is promoted, during entire experiment (32d), the dissolved oxygen concentration in covering treatment system is all much higher than at control
Reason, amplification is about 3mg/L.
5 oxygen micro-nano bubble of embodiment discharges influence of the granular activated carbon covering to Taihu Lake simulation column water/sediment interface ORP
It takes cocoanut active charcoal (2-5mm), deionized water sufficiently washs and washes out powdered active carbon, in 80 after bleeding water
DEG C drying overnight, handles 12h, pressure is less than -0.095MPa, by simulation column after cooling in 90 DEG C of vacuum oven after taking-up
Quality thin layer needed for size weighs up covering 5cm active carbon, which is placed in Vacuum pressure swing adsorption equipment, to be handled, and vacuum condition is set
It is set to -0.09MPa 2h, O2High Pressure Absorption condition is 0.15MPa 0.5h, circulating vacuum transformation operating procedure 3 times, and last
Sub-high pressure equilibration time is no less than 12h.Deposit and lake water are derived from the area that Jiangsu Province's Lake Taihu algal tufa often accumulates, will
It is transferred to laboratory and fills column, pillar long 0.5m, internal diameter 90mm, the high 10cm of deposit, overlying water depth 35cm after deploying uniformly.
Pillar is stablized 2 weeks at room temperature after installing.Experiment is adjusted the initial DO concentration of overlying water to the left side 2mg/L with nitrogen before starting
It is right.Micro-nano bubble releasable material is depressured again before application, and uniform fold is in simulation column immediately after taking-up, in order to reduce overlying water
Oxygen between atmosphere exchanges, and seals simulation column with sealed bag after covering 2d, as a result sees Fig. 5.As seen from the figure, the oxygen of 5cm thickness
Micro-nano bubble release active carbon covering can reverse the oxidation-reduction potential of water/sediment interface in a short time, by ORP from first
- 100mV to begin or so is reversed to+200mV or more, and can be held at+100mV or more during entire experiment, and testing
At the end of 96d stablize in+200mV or so, and the ORP of control treatment then has obvious downward trend, terminates in experiment
When 96d stablize below -200mV.The schematic diagram that micro-nano bubble releasable material repairs natural water body is shown in Fig. 6.
The above description is only an embodiment of the present invention, is not intended to restrict the invention.The present invention can have various conjunctions
Suitable change and variation.Any modification, equivalent substitution, improvement and etc. done within the spirit and principles of the present invention, should all
It is included within protection scope of the present invention.
Claims (12)
1. a kind of micro-nano bubble releasable material for natural water body reparation, which is characterized in that micro-nano bubble is immersed in material
It is generated after water body, had both included the body phase micro-nano bubble being distributed in overlying water, and also included the interface fixed by material
Micro-nano bubble, efficient fast oxygenation which can be realized simultaneously overlying water and the oxidation of anoxic sediments object-water termination are also
The long-acting reverse of former current potential, in addition, the reductive pollutants that the oxygen-containing coating of material can be also effectively isolated in deposit are upward
Cover water release.
2. a kind of micro-nano bubble releasable material for natural water body reparation, which is characterized in that the side of natural subsidence can be passed through
Body phase and interface micro-nano bubble are transported to deposit surface by formula.
3. a kind of micro-nano bubble releasable material for natural water body reparation, which is characterized in that material therefor is porous material,
It can be the active carbon that processing is formed, be also possible to clay or mineral, such as zeolite, local soil, pelelith, diatomite, swelling
The one or more of soil, kaolin, concave convex rod, sepiolite, montmorillonite etc..
4. material according to claim 3, which is characterized in that micro-nano can be regulated and controled by controlling the hydrophilic and hydrophobic of material
The quantity of bubble, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles.
5. material according to claim 3, which is characterized in that the size and intensive journey in control material surface hole can be passed through
It spends to regulate and control the quantity, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles of micro-nano bubble.
6. material according to claim 3, which is characterized in that micro-nano can be regulated and controled by controlling the specific surface area of material
The quantity of bubble, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles.
7. material according to claim 3, which is characterized in that micro-nano can be regulated and controled by controlling the particle size of material
The quantity of bubble, size, the fixed efficiency of the release time of body phase bubble and interfacial bubbles.
8. a kind of micro-nano bubble releasable material for natural water body reparation, which is characterized in that the gas source of micro-nano bubble can be
Oxygen, ozone, air, gaseous mixture of above-mentioned gas etc. contain the gas of a certain amount of oxygen.
9. a kind of preparation of the micro-nano bubble releasable material for natural water body reparation, which is characterized in that can be by vacuumizing
Mode the initial gas of material surface is desorbed, then so that object gas is loaded to porous material by way of High Pressure Absorption
In.
10. material according to claim 9, which is characterized in that can be adjusted by controlling the pressure of High Pressure Absorption process
Control the production quantity of micro-nano bubble.
11. material according to claim 9, which is characterized in that material before supporting gas will by high temperature, vacuumize or
The modes such as high-temperature vacuum sufficiently remove the moisture in material.
12. material according to claim 9, which is characterized in that material is before application again from vacuum pressure swing adsorption apparatus
It takes out, exists side by side and use.
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| CN110711552A (en) * | 2019-11-14 | 2020-01-21 | 中国科学院北京综合研究中心 | Synchronous denitrification dephosphorization oxygenation composite material and preparation method and application thereof |
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| CN111905690A (en) * | 2020-08-10 | 2020-11-10 | 重庆大学 | Method for preparing water body nitrogen and phosphorus removal oxygenation composite material by utilizing coal ash |
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| CN114291985A (en) * | 2021-12-08 | 2022-04-08 | 南京中科水治理股份有限公司 | Method for inhibiting release of endogenous nitrogen and phosphorus in bottom sediment |
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Application publication date: 20190816 |