CN108483623B - Oxygen slow-release material for improving water body bottom environment and preparation method and preparation device thereof - Google Patents
Oxygen slow-release material for improving water body bottom environment and preparation method and preparation device thereof Download PDFInfo
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- CN108483623B CN108483623B CN201810311986.2A CN201810311986A CN108483623B CN 108483623 B CN108483623 B CN 108483623B CN 201810311986 A CN201810311986 A CN 201810311986A CN 108483623 B CN108483623 B CN 108483623B
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- 239000001301 oxygen Substances 0.000 title claims abstract description 104
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 104
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 13
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- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
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- 239000004575 stone Substances 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000003911 water pollution Methods 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000007788 liquid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
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- 238000005273 aeration Methods 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004343 Calcium peroxide Substances 0.000 description 3
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- 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
- C02F3/02—Aerobic processes
- C02F3/025—Biological purification using sources of oxygen other than air, oxygen or ozone
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the field of water pollution treatment, in particular to an oxygen slow-release material for improving the environment at the bottom of a water body, and a preparation method and a preparation device thereof. The oxygen-enriched porous medium comprises a porous medium and a wrapping layer, and is characterized by also comprising oxygen in pores of the porous medium, wherein the wrapping layer wraps the surface of the porous medium to seal the oxygen in the pores of the porous medium. The pores of the porous medium are used as an oxygen carrier, and pure oxygen is used as an oxygen source, so that the oxygen slow-release material is not generated by strong oxidizing and alkaline substances when being thrown into a water body, and the growth and the propagation of microorganisms and plants are facilitated; meanwhile, the adopted coating layer can slowly release oxygen, and dissolved oxygen put into the bottom of the water body can keep a certain level within a plurality of days, so that an aerobic environment is continuously provided for plants and microorganisms. The invention also provides a preparation method and a preparation device of the slow-release oxygen material.
Description
Technical Field
The invention relates to the field of water pollution treatment, in particular to an oxygen slow-release material for improving the environment at the bottom of a water body, and a preparation method and a preparation device thereof.
Background
Along with the development of economy, the water pollution is increasingly serious, and the distribution of black and odorous water is wider and wider. For the treatment of black and odorous water, besides controlling endogenous and exogenous pollutants, the construction of a water body ecological system is implemented, the self-cleaning capacity of the water body is improved, the method is a fundamental way for ensuring long-term and lasting restoration effect, and the dissolved oxygen level in the water body is a key factor for limiting the recovery of submerged plants in the water body ecological system. The dissolved oxygen level of the water body is increased, the microbial habitat of the water body can be improved, the activity of aerobic microorganisms in the water is enhanced, the population quantity of the aerobic microorganisms is increased, the degradation of the microorganisms to organic pollutants is effectively promoted, the germination, the growth and the propagation of aquatic plants can be promoted, oxygen is further released through the photosynthesis of the plants, the dissolved oxygen is increased, organic matters such as N, P are absorbed and converted, and the ecological environment of the water body is gradually improved.
The existing method for improving the dissolved oxygen in the water body mainly adopts physical aeration, and is widely applied to the field of various sewage treatment. Aeration is mainly divided into spraying liquid in air (such as a biological filter); diffusing air bubbles in the liquid (e.g., blast aeration); three modes of renewing liquid surface and making air transfer to liquid phase at interface (such as mechanical aeration) are adopted. However, the application of aeration to a wide range of natural waters such as rivers and lakes is limited by various factors, such as the site of the method, the scale of the equipment, the transportation and assembly of the equipment, the power supply and distribution, and the running cost.
Based on the limitation of factors such as persistence and energy consumption of the increase of dissolved oxygen in water by a physical method, the construction of oxygen slow release materials is gradually increased in recent years, the existing method mainly comprises the steps of constructing a slow release embedding medium and coating chemical substances which potentially generate oxygen in the slow release embedding medium, wherein the substances react to release oxygen after being dissolved in water, but due to the limitation of a coating layer, the oxygen release rate is controllable, so that the slow oxygen release can be realized to a certain extent. For example, the patent "a preparation method of oxygen slow release agent for repairing polluted site (CN 104560051 a)," a slow release oxidant using calcium peroxide as matrix attapulgite as coating and its preparation method (CA 105820822A), "a slow release oxidant using calcium peroxide as matrix ethylcellulose as coating and its preparation method (CN 105925267 a)," an oxygen release filler for repairing underground water pollution aerobic organism (CN 103214086A) "and so on (including but not limited to the above patents) are all based on the above principle. However, since the oxygen slow-release material contained in the coating layer is a chemical agent, the oxygen slow-release material can raise the pH value of the water body while generating oxygen when reacting with water, and potential negative ecological effects can be caused. For example, hydrogen peroxide is a strong oxidant and will cause damage to various animals, plants, microorganisms and the like in natural water, and calcium peroxide is nontoxic, but the product after reaction with water is calcium hydroxide which is moderate and strong alkali and can greatly affect the pH value of a water area, thereby further causing great influence on water ecology.
On this basis, in order to avoid the possible negative effects of chemical agents on water ecology, some patents have attempted to increase the dissolved oxygen level in water bodies by using the physical oxygen carrying properties of certain materials (e.g., a chlorite suspension rich in microaerophilic bubbles and a method for removing odoriferous substances from anaerobic water bodies by using the chlorite-loaded microaerophilic bubbles, CN 103626279 a). The method has small influence on water ecology, but the oxygen carrying capacity is limited, and under the interference of river hydrodynamic force, oxygen loaded on the material is quickly released, so that the long-time repair of a river/lake sediment system is difficult.
Disclosure of Invention
In order to solve the above problems, in a first aspect, the present invention provides an oxygen slow release material for improving a water bottom environment, wherein the oxygen carrying capacity is 4 to 20mg/kg, oxygen release compounds such as calcium hydroxide and hydrogen peroxide are not required, adverse effects on the water bottom environment are not caused, the dissolved oxygen content of the water bottom environment can be maintained within several days, and the water bottom environment is improved.
An oxygen slow release material for improving the bottom environment of a water body comprises a porous medium and a wrapping layer, and is characterized by further comprising oxygen in pores of the porous medium, wherein the wrapping layer wraps the surface of the porous medium to seal the oxygen in the pores of the porous medium.
Furthermore, the particle size of the slow release material is 2-5 mm, the particle size of the porous medium is 1.5-4 mm, the thickness of the wrapping layer is 0.5-2 mm, the pore diameter of the porous medium is 1-10000 nm, and the pore volume range is 0.02-0.90 mL/g.
Further, the wrapping layer is a membrane made of one or more of chitosan, agar, xanthan gum, gelatin, chitin, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and sodium alginate.
Further, the wrapping layer is a film which is prepared from/made of chitosan, acrylamide, acrylic acid, ammonium persulfate, sodium hydroxide, sodium chloride, hydrochloric acid, glutaraldehyde and N, N-methylene bisacrylamide, and is/is prepared from/made of polyvinylpyrrolidone and polyvinyl alcohol.
Further, the mass ratio of the chitosan to the polyethylene glycol to the sand grains with the grain diameter of 0.25-0.5 nm is 3:1: 5.
Further, the porous medium is active carbon, zeolite, medical stone and diatomite.
The activated carbon can be various materials, such as wood activated carbon, animal bone/blood activated carbon, mineral raw material activated carbon, other raw material activated carbon and regenerated activated carbon which are prepared by a chemical method, a physical method, a chemical-physical method or a physical-chemical method, such as coal, wood, nut shells, coconut shells, walnut shells, apricot shells, jujube shells and the like. The appearance shape of the carbon can be powder activated carbon, granular activated carbon, amorphous activated carbon, cylindrical activated carbon, spherical activated carbon or activated carbon with other shapes.
In a second aspect, the invention also provides a preparation method of the oxygen slow-release material for improving the bottom environment of the water body.
A preparation method of an oxygen slow release material for improving the bottom environment of a water body comprises the following three steps:
step 1: placing the porous medium in a closed container, vacuumizing the closed container, removing air in pores of the porous medium, and stopping vacuumizing when the pressure in the closed container is reduced to be constant;
step 2: filling oxygen into the closed container, filling the oxygen into the pores of the porous medium, and stopping filling the oxygen when the pressure in the closed container reaches 0.096-0.4 MPa;
and step 3: weighing the raw materials of the coating layer according to the proportion, adding an organic solvent, heating, stirring and dissolving to form a coating liquid, adding the coating liquid into a closed container, mixing with a porous medium, heating and maintaining the temperature in the container, stirring, and coating the coating liquid on the porous medium to form the coating layer, thus obtaining the oxygen slow-release material.
Further, in the step 3, the coating layer is prepared from chitosan, polyethylene glycol and sand particles in a mass ratio of 3:1:5, the organic solvent is carbon tetrachloride, and the heating temperature is 20-80 ℃.
In a third aspect, the invention also provides a preparation device of the oxygen slow-release material for improving the bottom environment of the water body.
The utility model provides an improve preparation facilities of oxygen sustained-release material of water bottom environment, includes reation kettle, oxygen cylinder, adds medicinal cupping and vacuum pump, and the oxygen cylinder is linked together through the pipeline that is equipped with the valve with reation kettle, and reation kettle is linked together through the pipeline that is equipped with the valve with the vacuum pump, adds the medicinal cupping and is linked together through the pipeline that is equipped with the valve with reation kettle, is equipped with the agitating unit of stirring material and the heating device of heating material in the reation kettle, is equipped with the manometer of survey reation kettle internal pressure on the reation kettle.
The preparation device works by placing the porous medium in a reaction kettle, opening a vacuum pump, closing the vacuum pump and a valve between the vacuum pump and the reaction kettle when the pressure reading in the reaction kettle is zero, opening a valve between an oxygen cylinder and the reaction kettle, inputting oxygen into the reaction kettle, closing the valve after the pressure displayed by a pressure gauge reaches a certain value, and completely replacing air in the pores of the porous medium with pure oxygen at the moment. And then opening a valve between the medicine adding tank and the reaction kettle, inputting the wrapping liquid into the reaction kettle, starting a stirring device of the reaction kettle, opening a heating device to maintain the temperature at a certain temperature, closing the stirring device and the heating device after stirring for a period of time, and opening the reaction kettle after standing to obtain the material with the functions of high-efficiency oxygen carrying and slow oxygen release.
The invention has the beneficial effects that:
1. according to the oxygen slow-release material provided by the invention, the pores of the porous medium are used as an oxygen carrier, and pure oxygen is used as an oxygen source, so that the oxygen slow-release material cannot generate strong oxidizing and alkaline substances when being thrown into a water body, and is favorable for growth and reproduction of microorganisms and plants; meanwhile, the adopted coating layer can slowly release oxygen, and dissolved oxygen put into the bottom of the water body can keep a certain level within a plurality of days, so that an aerobic environment is continuously provided for plants and microorganisms; after the oxygen slow release material releases oxygen, the pores of the porous medium can effectively adsorb pollutants in the water body, and the water body is purified.
2. The preparation method of the oxygen slow-release material provided by the invention is simple and rapid, can be operated in batches, and is beneficial to preparing the oxygen slow-release material in large scale.
3. The oxygen slow release material adopts polyethylene glycol, chitosan and sand grains as the raw materials of the coating layer, the chitosan can be biodegraded, the pores formed after degradation are beneficial to the release of oxygen, and the sand grains can increase the density of the oxygen slow release material and are beneficial to the sinking of the oxygen slow release material.
4. The preparation device provided by the invention is simple, compact and reasonable, and can be used for producing the oxygen slow-release material in batches.
Drawings
FIG. 1 is a flow chart of a method for preparing an oxygen-releasing material for improving the bottom environment of a water body;
FIG. 2 is a schematic structural diagram of a device for preparing an oxygen slow-release material for improving the bottom environment of a water body;
FIG. 3 is a schematic diagram of an oxygen slow release material cooperating with submerged plants to improve the sediment-water interface oxygen environment;
FIG. 4 is a graph of the DO concentration change of the sediment-water interface oxygen environment improved by the oxygen slow release material in cooperation with the submerged plant.
In FIG. 2, 1-oxygen cylinder; 2-a reaction kettle, 21-a pressure gauge, 22-a stirring device and 23-a heating device; 3-adding a medicine tank; 4-vacuum pump.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
An oxygen slow release material for improving the bottom environment of a water body comprises a porous medium, a wrapping layer and oxygen in pores of the porous medium, wherein the wrapping layer wraps the surface of the porous medium to seal the oxygen in the pores of the porous medium. The coating layer is composed of chitosan, polyethylene glycol and sand grains, and the mass ratio of the chitosan to the polyethylene glycol to the sand grains is 3:1: 5. The porous medium is activated carbon.
The device for preparing the oxygen slow release material is shown in figure 2 and comprises a reaction kettle 2, an oxygen bottle 1, a dosing tank 3 and a vacuum pump 4, wherein the oxygen bottle 1 is communicated with the reaction kettle 2 through a pipeline provided with a valve, the reaction kettle 2 is communicated with the vacuum pump 4 through a pipeline provided with a valve, the dosing tank 3 is communicated with the reaction kettle 2 through a pipeline provided with a valve, a stirring device 22 and a heating device 23 for stirring materials are arranged in the reaction kettle 2, and a pressure gauge 21 for measuring the pressure in the reaction kettle is arranged on the reaction kettle.
The method for preparing the oxygen slow release material comprises the following steps:
step 1: putting the activated carbon into a reaction kettle 2, starting a vacuum pump 4 to vacuumize the reaction kettle, removing air in pores of the porous medium, closing a valve when the pressure in the reaction kettle 2 is constant, and stopping vacuumizing;
step 2: opening an oxygen bottle 1 and a valve, filling oxygen into a reaction kettle 2, filling the oxygen into pores of activated carbon, stopping filling the oxygen when the pressure in the reaction kettle reaches 0.096MPa, and closing the valve;
and step 3: weighing the raw materials of the wrapping layer according to the proportion: adding carbon tetrachloride accounting for 10% of the volume of the raw materials into chitosan, polyethylene glycol and sand, heating to 25 ℃, stirring and dissolving to form a coating liquid, adding the coating liquid into a medicine adding tank 3, opening a valve, allowing the coating liquid to enter a reaction kettle 2, opening a heating device, heating to maintain the temperature in the reaction kettle 2 at 25 ℃, stirring for 40 minutes, closing a heating device 23 and a stirrer 22, standing for 6 hours, and opening the reaction kettle 2 to obtain the oxygen slow-release material.
In order to examine the oxygen release effect of the oxygen slow release material, a sediment columnar sample collected from a bittersweet (black and odorous river) in situ in Chongqing city is brought back to a laboratory and is set to be treated as follows: 5kg of sediment in-situ columnar sample, 5kg of sediment +30g of oxygen slow-release material coverage (a in figure 3), 5kg of sediment +30g of green high-efficiency oxygen slow-release material coverage + submerged plant tape grass seeds (b in figure 3), and determining the change of DO concentration in the treated water body. The change curve is shown in fig. 4, the DO at the sediment-water interface can be obviously improved by introducing the oxygen slow-release material until the DO in the material is completely released after 15 days (at the moment, the DO at the sediment-water interface is 8.4mg/L), and then the DO is reduced until the DO is equal to the DO slow-release material added; after the submerged plants are introduced, DO in the water body keeps higher level in a test period of 60 days, and DO at a sediment-water interface is still maintained at 7.9mg/L at the 60 th day.
Claims (6)
1. An oxygen slow release material for improving the bottom environment of a water body comprises a porous medium and a wrapping layer, and is characterized by also comprising oxygen in pores of the porous medium, wherein the wrapping layer wraps the surface of the porous medium to seal the oxygen in the pores of the porous medium; the wrapping layer is a film made of one or more of chitosan, agar, xanthan gum, gelatin, chitin, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and sodium alginate;
the preparation method specifically comprises the following steps:
step 1: placing the porous medium in a closed container, vacuumizing the closed container, removing air in pores of the porous medium, and stopping vacuumizing when the pressure in the closed container is reduced to be constant;
step 2: filling oxygen into the closed container, filling the oxygen into the pores of the porous medium, and stopping filling the oxygen when the pressure in the closed container reaches 0.096-0.4 MPa;
and step 3: weighing the coating raw materials according to the proportion, wherein the mass ratio of the coating raw materials to the porous medium is 1: 2-5, adding an organic solvent, heating and stirring to dissolve the coating raw materials to form a coating solution, adding the coating solution into a closed container to mix with the porous medium, heating to maintain the temperature in the container, stirring, and coating the coating solution on the porous medium to form a coating layer, thus obtaining the oxygen slow-release material.
2. The oxygen slow-release material according to claim 1, wherein the slow-release material has a particle size of 2 to 5mm, the porous medium has a particle size of 1.5 to 4mm, the coating layer has a thickness of 0.5 to 2mm, and the porous medium has a pore diameter of 1 to 10000nm and a pore volume of 0.02 to 0.90 mL/g.
3. The oxygen-releasing material according to claim 1, wherein said coating layer is a film made of chitosan, polyethylene glycol and sand particles having a particle size of 0.25 to 0.5mm, or made of polyvinylpyrrolidone and polyvinyl alcohol, or made of chitosan, acrylamide, acrylic acid, ammonium persulfate, sodium hydroxide, sodium chloride, hydrochloric acid, glutaraldehyde and N, N-methylenebisacrylamide.
4. The oxygen slow-release material according to claim 3, wherein the mass ratio of the chitosan to the polyethylene glycol to the sand particles with the particle size of 0.25-0.5 nm is 3:1: 5.
5. The oxygen-eluting material of claim 2, wherein the porous medium is activated carbon, zeolite, medical stone, diatomaceous earth.
6. The oxygen slow-release material according to claim 4, wherein in the step 3, the coating layer is prepared from chitosan, polyethylene glycol and sand with a particle size of 0.25-0.5 nm, the mass ratio of the chitosan to the polyethylene glycol to the sand is 3:1:5, the organic solvent is carbon tetrachloride, and the heating temperature is 20-80 ℃.
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| CN104560051A (en) * | 2013-10-12 | 2015-04-29 | 中环循(北京)环境技术中心 | Preparation method of oxygen slow release preparation for repairing of contaminated site |
| CN103626279B (en) * | 2013-12-11 | 2015-06-10 | 中国科学院南京地理与湖泊研究所 | Chlorite suspension rich in micro-aerobic bubbles and method for removing odor-causing pollutants in anaerobic water body by utilizing chlorite loaded with micro-aerobic bubbles |
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