CN111056615B - Method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide - Google Patents
Method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000005422 algal bloom Substances 0.000 title claims abstract description 23
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- 108700012359 toxins Proteins 0.000 claims description 58
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- RPQXVSUAYFXFJA-HGRQIUPRSA-N saxitoxin Chemical compound NC(=O)OC[C@@H]1N=C(N)N2CCC(O)(O)[C@@]22N=C(N)N[C@@H]12 RPQXVSUAYFXFJA-HGRQIUPRSA-N 0.000 claims description 2
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- 241000251468 Actinopterygii Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241000235819 Cytospora Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002063 effect on algae Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide. The method comprises the following steps: adding hydrogen peroxide into the water body suffering from algal bloom or red tide, and immediately performing primary ultraviolet source irradiation; after the first irradiation of the ultraviolet source, stopping the irradiation for intermittence, and then performing the second irradiation of the ultraviolet source, thereby realizing the treatment of algal bloom or red tide. The method can effectively improve the inactivation effect of the algae cells, shorten the time required for effect, reduce the dosage of the medicament, and does not produce harmful byproducts in the treatment process, thereby being environment-friendly.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide, which is suitable for preventing and controlling algal bloom or red tide in various eutrophic water bodies such as lakes, reservoirs, rivers, ponds and oceans.
Background
Algal bloom or red tide is a phenomenon that algae are excessively propagated after nutrient substances such as nitrogen and phosphorus in a water body are excessive and a eutrophication state is presented. Algae that have been documented to form blooms or red tides include blue algae, green algae, diatoms, dinoflagellates, chrysophytes, conidiophores, dinoflagellates, and the like. Algae bloom or red tide consumes nutrient substances in a water body, and the death process of algae consumes dissolved oxygen in the water body, so that other aquatic animals and plants die. Some algal blooms produce algal toxins, which can cause symptoms of liver poisoning, respiratory paralysis, vomiting, diarrhea, nervousness and the like of aquatic animals, human beings and livestock, and even death. Algal blooms or red tides frequently occur in lakes, reservoirs, rivers and oceans, and serious challenges are brought to the protection of water supply sites, the treatment of water supply, the aquaculture and the marine environment.
The common algae bloom or red tide treating technology includes physical method, chemical method, biological method, etc. Physical methods such as coagulating sedimentation, membrane separation and the like have good separation effect on algae cells, but have poor inactivation effect and almost no removal effect on extracellular algal toxins. Ultraviolet radiation can penetrate through algae cells to attack intracellular nucleic acid, photosynthetic system and other sites to inhibit the growth of the algae cells, but the ultraviolet dose required for inactivating the algae cells is higher, seeThe effect is slower. Chemical methods such as potassium permanganate, sodium hypochlorite, chlorine dioxide, ozone and the like can effectively inactivate algae cells and have certain oxidative decomposition capacity on algal toxins. However, most of the chemical agents do not enter the algal cells and are mostly consumed in oxidizing and damaging the external structures of the algal cells, so that the dosage of the agents required for inactivating the algal cells is high. H2O2Can enter the interior of algae cells, can quickly and effectively inhibit the growth of algae, has small influence on other aquatic animals and plants and lower secondary pollution risk, is an environment-friendly algae inhibitor, and still has the problem of insufficient inactivation effect of the algae cells. Biological methods utilize feeding of organisms such as fish to realize biological manipulation or algae cell death induction by utilizing algicidal bacteria, but the time consumption is long.
Advanced oxidation processes such as UV/H2O2The combination, the ultraviolet/chlorine combination, the ultraviolet/persulfate combination and the like utilize ultraviolet radiation to excite to generate free radicals with strong oxidizing property, so as to oxidize and decompose algae cells and algae toxins, and improve the inactivation rate and the speed of the algae cells. ultraviolet/H2O2A radical OH having a strong oxidizing property is used in combination. There is a patent application for ultraviolet/H2O2The combination removes the algae and the toxins and smelly substances produced by the algae, such as CN108358273A, CN109896583A and CN 105540732B. But simultaneously applying ultraviolet rays and H2O2The generated free radical OH is positioned outside the algae cells, and the characteristic of rapid quenching of the free radical OH causes the free radical OH to only attack the external structure of the algae cells, has small influence on the internal structure of the algae cells, and has slow effect on inactivating the algae cells. In addition, organic matter in water can affect the penetration of ultraviolet light and compete for the consumption of free radicals, OH, resulting in ultraviolet light and H required to inactivate algal cells2O2The dosage is higher, which affects the large-scale use.
Disclosure of Invention
In order to solve the drawbacks of the prior art, the invention is based on the reduction of UV and H2O2Dosage, ultraviolet ray and H are increased2O2Combines the requirements of inhibiting the algal bloom and innovatively provides an intermittent combined treatment method of algal bloom or red tide by ultraviolet rays and hydrogen peroxideA method. The invention also aims to provide the application of the method in treating algal bloom or red tide.
The purpose of the invention is realized by the following technical means:
in one aspect, the invention provides a method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide, which comprises the following steps:
adding hydrogen peroxide into the water body suffering from algal bloom or red tide, and immediately performing primary ultraviolet source irradiation; after the first irradiation of the ultraviolet source, stopping the irradiation for intermittence, and then performing the second irradiation of the ultraviolet source, thereby realizing the treatment of algal bloom or red tide.
In the invention, the inventor researches and discovers that the first ultraviolet source irradiation is carried out immediately after hydrogen peroxide is added into water body with algal bloom or red tide, and H is2O2The method can generate free radicals OH with strong oxidizing property under the excitation of an ultraviolet source, the free radicals OH can damage the external structure of algae cells through oxidation, remove extracellular algal toxins and organic matters influencing the transmittance of the ultraviolet source in water, and improve the ultraviolet transmittance of the water body. Batch treatment, part H, before the second UV source irradiation2O2Enter into algae cells in the intermittence period to become intracellular H2O2. Immediately after the end of the rest period, a second UV irradiation is carried out, with intracellular H2O2The method can generate intracellular free radical OH with strong oxidizing property in cells under the excitation of an ultraviolet source, the intracellular free radical OH can damage organelles and contents of algae cells and degrade intracellular algae toxins, the step can efficiently inactivate the algae cells and remove the intracellular algae toxins, the inactivation effect and the degradation effect of the algae cells are higher than those of a traditional advanced oxidation method, and the required medicament dosage is obviously lower than that of the traditional advanced oxidation method for realizing cell lysis by destroying the external structure of the algae cells.
In the invention, the algae bloom is treated by intermittently combining ultraviolet rays and hydrogen peroxideOr red tide, ensures that hydrogen peroxide exists both intracellularly and extracellularly through intermittent treatment, and utilizes ultraviolet rays generated by an ultraviolet ray source to excite H2O2The strong oxidative free radical OH is generated by exciting an extracellular free radical or an intracellular free radical inside a cell.
The method provided by the invention can be used for treating all or part of the area of the water body.
In the above process, H2O2The free radicals OH with strong oxidizing property are generated under the excitation of ultraviolet rays, and oxidize organic matters in water to improve the ultraviolet transmittance of the water body, which means that organic matter molecules are oxidized into two or more than two small molecules by OH or ultraviolet absorption groups of the organic matters are oxidized and destroyed by OH, so that the ultraviolet absorption capacity of the water body is reduced, and the ultraviolet transmittance of the water body is improved.
In the above method, part H is used during the interval between the first and second irradiation with ultraviolet light source2O2Will enter into algae cell to become intracellular H2O2This means that exogenous H is added2O2The aquaporins are transported into the algal cells through the algal cell membrane and accumulate to a certain concentration. Intracellular H2O2Can generate strong oxidative intracellular free radical OH in cells under the excitation of ultraviolet rays, and the intracellular free radical OH damages organelles and contents of algae cells and degrades intracellular algal toxins. The algae cells are inactivated by inducing intracellular free radicals OH to form algae cell internal damage, the algae cell inactivation effect and the algae toxin degradation effect are higher than those of the traditional advanced oxidation method, and the required medicament dosage is obviously lower than that of the traditional advanced oxidation method for realizing cell lysis by destroying the external structure of the algae cells.
In the above method, preferably, when two times of irradiation of the ultraviolet source are adopted, the total dose irradiated by the ultraviolet source is 20-300 mJ-cm-2(ii) a The total dosage concentration of the hydrogen peroxide is 0.01-1 mmol/L. mJ.cm-2Is a standard unit of ultraviolet intensity, and refers to a unit area of water body treated by ultravioletFor example, for an ultraviolet reactor, water flows into the reactor, the area being the cross-sectional area perpendicular to the ultraviolet lamp tube; if the ultraviolet lamp tube matrix is used, the area is the cross-sectional area of water vertical to the ultraviolet lamp tube.
In the above method, preferably, when two times of ultraviolet irradiation are adopted, the dose of the first ultraviolet irradiation is 20-50% of the total dose of the ultraviolet irradiation; the dosage can efficiently remove extracellular algal toxins, improve the ultraviolet transmittance of a water body and cause certain damage to external structures of algal cells; the dose for implementing the second time of ultraviolet source irradiation is 50 to 80 percent of the total dose of ultraviolet source irradiation; the dosage can effectively inactivate algae cells and remove intracellular algal toxins.
In the above method, the time interval between the first irradiation and the second irradiation is preferably 5 to 60min, and more preferably 5 to 30 min.
In the above method, preferably, after the second irradiation with the uv source is performed, if residual algal toxins still remain in the water after algal cells are ruptured and dead, hydrogen peroxide is further added to the water body, and the third irradiation with the uv source is performed. If necessary, after the third irradiation with the ultraviolet source, the irradiation with the ultraviolet ray may be continued more than once. Residual extracellular algal toxin can be removed efficiently by applying a third irradiation of ultraviolet light source. Wherein the dose for implementing the third time of ultraviolet source irradiation is 20-100 mJ-cm-2(ii) a The dosage concentration of the added hydrogen peroxide is 0.01-0.2 mmol/L based on the volume of the treated water body.
According to a specific embodiment of the present invention, the water body to which the method of the present invention is directed (i.e., the water body subjected to algal bloom or red tide) may be a water body containing both algal cells and extracellular algal toxins.
According to a specific embodiment of the present invention, the algal cells in the water body are algae capable of forming a bloom or red tide, for example including one or more of blue algae, green algae, diatoms, dinoflagellates, chrysophyceae, sticocystis and dinoflagellates; the extracellular algal toxin contained in the water body is algal toxin which can cause one or more symptoms of liver poisoning, respiratory paralysis, vomiting and diarrhea, nervous confusion and/or death of aquatic animals, animals or livestock. Wherein the hepatotoxin can comprise one or more of microcystin, nodulotoxin and toxin of Cytospora; the neurotoxin can comprise one or more of anabaena toxin-a, saxitoxin, neosaxitoxin and gonyatoxin; the diarrheal toxin may include lipopolysaccharide endotoxin and/or finotoxin; the memory-deficit toxin may include domoic acid.
In the above method, the water containing both algal cells and extracellular algal toxins means that at least one algal cell can be detected and extracellular algal toxins can be detected in the water; the water can be either an environmental water body (including all water-covered surfaces of lakes, rivers, ponds, reservoirs, oceans, etc.) or water to be treated in a water treatment plant or water treatment facility.
In the above method, preferably, the uv source comprises the sun, or a device or apparatus capable of generating uv, especially a uv source capable of providing C-band uv; the device or apparatus capable of generating an ultraviolet source may include one or a combination of two or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a diode, an LED lamp, and the like.
When the sun is used as the ultraviolet source, the ultraviolet irradiation of the water body may be performed by exposing the water body to the irradiation of the sun, for example, by exposing a pool of water treatment facilities to sunlight. When a device or apparatus capable of generating ultraviolet rays is used as the ultraviolet source, any means capable of achieving the ultraviolet source can be used, for example, a means on board a ship is used, namely, the related device or apparatus is fixed on the ship, and ultraviolet irradiation on various areas of the water body is achieved through the movement of the ship.
According to the specific embodiment of the invention, the irradiation by using the ultraviolet source refers to the irradiation of ultraviolet rays into water, and the irradiation manner of the ultraviolet source can comprise the irradiation outside the water body and/or the irradiation inside the water body and the like, and the irradiation method comprises the steps that the equipment or the device for generating the ultraviolet source is contacted with water so that the ultraviolet rays directly enter the water body, and the ultraviolet rays indirectly enter the water body without being contacted with the water.
According to the specific embodiment of the present invention, the adding manner of the hydrogen peroxide may include directly adding the hydrogen peroxide or adding a chemical substance capable of generating the hydrogen peroxide. Wherein the chemical substance capable of generating hydrogen peroxide is generated by one or more of ionization, hydrolysis and oxidation, and the chemical substance can be directly added or specific H prepared by adding the chemical substance2O2A concentrated solution.
On the other hand, the invention also provides the application of the method in treating algal bloom or red tide.
The invention has the beneficial effects that:
the invention creatively provides an intermittent ultraviolet/H2O2The combined algae control method comprises the following steps of: during the first ultraviolet implementation period, strong oxidative free radicals OH can be excited in the water body, extracellular algal toxins can be efficiently removed through oxidation, and the ultraviolet transmittance of the water body is improved. A period of intermittent treatment is arranged between two times of ultraviolet irradiation, so that hydrogen peroxide with a certain concentration is accumulated in the algae cells, and during the second ultraviolet irradiation period, strong-oxidative free radicals & OH can be excited in the algae cells, so that the damage of important organelles such as nucleic acid, a photosynthetic system and the like in the algae cells is caused, and the external free radicals & OH attack the external structure of the algae cells to form internal and external dual attack, so that the algae cells are efficiently inactivated, and meanwhile, intracellular algae toxins are degraded. The algae cells are inactivated by inducing intracellular free radicals OH to form internal damage of the algae cells, and the dosage of the required medicament is obviously lower than that of the traditional advanced oxidation method for realizing cell lysis by destroying external structures of the algae cells, namely ultraviolet rays and H2O2The dosage of the composition is lower, and compared with the dosage used independently, the composition has the advantages of obvious reduction of cost and quick response.
The method does not produce harmful byproducts in the treatment process, does not cause new harm, and is environment-friendly; the application is flexible, and the method can be widely used for treating water containing algae cells. Therefore, the invention can effectively improve the inactivation effect of the algae cells, shorten the time required for effect, reduce the dosage of the medicament, and does not produce harmful byproducts in the treatment process, thereby being environment-friendly.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The present invention will be further described with reference to preferred embodiments.
The invention provides ultraviolet rays and H2O2A method for treating algal blooms or red tides in a batch combination, in some embodiments, the method comprises the steps of:
subjecting water body (containing algae cells and extracellular algal toxins) suffering from algal bloom or red tide to ultraviolet irradiation and H adding2O2The total dose of the ultraviolet rays is 20 mJ-cm in combined treatment-2～300mJ·cm-2Said H is2O2The concentration of (B) is 0.01 mM-1 mM. The intermittent ultraviolet radiation is implemented by two times, and the intermittent period is 5-60 min; preferably 5-30 min.
Adding H2O2Immediately thereafter, a first irradiation with UV light is carried out, H2O2Under the excitation of ultraviolet rays, strong oxidizing free radicals OH are generated, and the free radicals OH can oxidize and damage the external structure of algae cells, remove the extracellular algal toxins and remove organic matters affecting the ultraviolet transmittance in water. The first ultraviolet irradiation dose is 20-50% of the total ultraviolet dose. The step can efficiently remove extracellular algal toxins, improve the ultraviolet transmittance of the water body and cause certain damage to the external structure of algal cells.
Part H of the interval between the first and second UV light applications2O2Will enter into algae cell to become intracellular H2O2. This means that exogenous H is added2O2The aquaporins are transported into the algal cells through the algal cell membrane and accumulate to a certain concentration. Immediately after the end of the rest period, a second UV irradiation is carried out, with intracellular H2O2Under the excitation of ultraviolet rays, intracellular free radicals OH with strong oxidizing property are generated in cells, and damage organelles and contents of algae cells and degrade intracellular algal toxins. The second time ultraviolet irradiation dose is 50-80% of the total ultraviolet dose. The step can efficiently inactivate algae cells and remove intracellular algal toxins.
If residual algal toxin still exists in the water after the algal cells are broken and dead, starting ultraviolet/H again2O2Coupled treatment, H2O2Under the excitation of ultraviolet rays, strong oxidizing free radicals OH are generated, and the free radicals OH remove algal toxins in water. The ultraviolet radiation dose is 20-100 mJ-cm-2(ii) a The dosage concentration of the added hydrogen peroxide is 0.01-0.2 mmol/L based on the volume of the treated water body. The step can remove residual extracellular algal toxin with high efficiency.
Said H2O2The reaction formula of generating strong oxidizing radicals OH under the excitation of ultraviolet rays is as follows:
H2O2+hv→2·OH
the removal of the algal toxin by free radical OH oxidation means that algal toxin molecules are oxidized into two or more than two small molecules by OH.
The ultraviolet transmittance of the water body is improved by oxidizing organic matters in the water by the free radicals and OH, namely organic matter molecules are oxidized into two or more than two small molecules by the OH, or ultraviolet absorption groups of the organic matters are oxidized and destroyed by the OH, so that the ultraviolet absorption capacity of the water body is reduced, and the ultraviolet transmittance of the water body is increased.
The intermittent treatment for implementing ultraviolet rays means that ultraviolet irradiation is implemented twice, and the intermittent period is 5-60 min; preferably 5-30 min. The first ultraviolet irradiation dose is 20-50% of the total ultraviolet dose, and aims to efficiently remove extracellular algal toxins, improve the ultraviolet transmittance of a water body and damage external structures of algal cells to a certain extent. Applying ultraviolet rays for the first and second timesIn the rest period of (2), part H2O2Will enter into algae cell to become intracellular H2O2And accumulated to a certain concentration. On the basis of improving the ultraviolet transmittance of the water body, the second ultraviolet irradiation can more effectively enter the interior of the algae cells, so as to excite the H entering the cells2O2Intracellular free radicals OH with strong oxidizing properties are generated intracellularly, with the aim of efficiently inactivating algal cells and removing intracellular algal toxins.
The combined treatment is to direct ultraviolet irradiation in water and add H2O2Excitation of H by ultraviolet rays generated by an ultraviolet ray source2O2The strong oxidative free radical OH is generated by exciting an extracellular free radical or an intracellular free radical inside a cell. According to the specific algae species, biomass and extracellular endotoxin content in the target water body, the first ultraviolet irradiation dose and H2O2The dose is determined by taking the purposes of improving the ultraviolet transmittance of the water body and reducing the content of extracellular algal toxins as targets, and the dose of the second ultraviolet irradiation is determined by taking the purposes of realizing high algal cell inactivation rate and reducing the content of intracellular algal toxins as targets. The invention provides that the dosage range of the ultraviolet ray is 20 mJ-cm based on the test of common water bloom, red tide algae and algal toxin-2～300mJ·cm-2Said H is2O2The concentration range of (A) is 0.01 mM-1 mM, and the intermission period range is 5-60 min; preferably 5-30min, and the dosage of the medicament can be further optimized and determined according to the actual condition of the target water body and the steps.
The water containing both algal cells and extracellular algal toxins means that at least one algal cell can be detected and extracellular algal toxins can be detected in the water. The water may be either an environmental body of water (including all surfaces covered by water in lakes, rivers, ponds, reservoirs, oceans, etc.) or water from a water treatment plant or facility.
The algae cells contained in the water are algae capable of forming water bloom or red tide, and include blue algae, green algae, diatom, dinoflagellate, chrysophyceae, stipulophyceae, dinoflagellate, etc. The algae toxin contained in water can cause symptoms of liver poisoning, respiratory paralysis, vomiting and diarrhea, nerve disorder and the like of aquatic animals, human beings and livestock, and even cause death.
H in the examples of the present invention2O2The ultraviolet ray is easy to obtain and flexible to apply, and the generation source of the ultraviolet ray can be the sun or all equipment or devices capable of generating the ultraviolet ray (for example, the ultraviolet ray equipment or devices which can be moved, disassembled and assembled or fixed are erected, or the ultraviolet ray equipment or devices are additionally arranged on the original water treatment equipment, devices and facilities, or the newly-built ultraviolet ray equipment is also adopted). The device or apparatus for generating the ultraviolet source includes all devices or apparatuses capable of generating the ultraviolet source, such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a diode, and an LED.
The irradiation by using the ultraviolet source refers to the irradiation of ultraviolet rays into water, and comprises the steps that the equipment or the device for generating the ultraviolet source is contacted with water so that the ultraviolet rays directly enter the water body, and also comprises the steps that the ultraviolet rays indirectly enter the water body without being contacted with the water.
H added2O2All the components are added to generate H through ionization, hydrolysis, oxidation and the like2O2The chemical substance(s) can be directly added or added to a specific concentration H2O2The solution of (1).
The invention is further illustrated by the following two preferred examples.
Example one
The embodiment provides a method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide, which comprises the following steps:
water bloom index: the water contains microcystis aeruginosa and microcystin, and the cell density of the algae in the water is detected. Wherein, the algal cell density is directly detected by a flow cytometer, and the algal toxin concentration is detected by LC/MS/MS.
Ultraviolet ray and H2O2The mode of combined treatment was divided into three as shown in table 1.
Mode one is synchronous ultraviolet/H2O2Combined, i.e. ultraviolet with H2O2All are disposable. Adding a certain amount of H when starting irradiation2O2Solution of H2O2To a final concentration of 0.025 mM. Opening ultraviolet quasi-parallel light beam instrument, irradiating water containing algae cells and extracellular algal toxin with ultraviolet dose controlled at 150 mJ-cm-2。
Mode two lagging UV/H2O2Combined, i.e. adding H first2O2Until the concentration is 0.025mM, opening ultraviolet quasi-parallel light beam instrument at an interval of 10min, and irradiating water containing algae cells and extracellular algal toxin with ultraviolet dose controlled at 150 mJ-cm-2。
Mode three is intermittent UV/H2O2The combination is used. H2O2The dose was controlled at 0.025 mM. Two different groups of ultraviolet dose distribution treatments are set, and the total ultraviolet dose is 150mJ cm-2The first and second UV doses of the first batch combination I were 25% and 75% of the total amount, respectively, and the first and second UV doses of the second batch combination II were 50% of the total amount. In this example, H was added2O2When the concentration is 0.025mM, the ultraviolet quasi-parallel light beam instrument is immediately turned on to carry out the first ultraviolet irradiation, and the doses are respectively 37.5mJ cm-2And 75 mJ. cm-2Accounting for 25% and 50% of the total UV dose. After 10min, the ultraviolet quasi-parallel light beam instrument is opened again to perform the second ultraviolet irradiation with the dose of 112.5mJ cm-2And 75 mJ. cm-275% and 50% of the total UV dose. Setting observation period as 40d, sampling at 40d and using Na2S2O3The oxidizing agent is quenched for detection. Set up 3 sets of replicates. The results of the experiment are shown in table 1.
TABLE 1
The test results in table 1 show that compared with the synchronous combination (removal rate of 42.7-71.8%) and the hysteresis combination (removal rate of 82.4-87%), the intermittent combination method of the invention has the advantages that the removal rate of 99.5-99.7% is high, and the method is obviously superior to other treatment methods.
Example two
The embodiment provides a method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide, which comprises the following steps:
water bloom index: the water contains microcystis aeruginosa and microcystin, and the cell density of the algae in the water is detected. Wherein, the algal cell density is directly detected by a flow cytometer, and the algal toxin concentration is detected by LC/MS/MS.
Ultraviolet ray and H2O2The processing patterns are classified into three categories as shown in table 2.
The control group was samples without any treatment.
The ultraviolet treatment group is to irradiate water containing algae cells and extracellular algal toxins with ultraviolet rays only, and the dose of the ultraviolet rays in the two groups is set to be 50 mJ-cm-2And 150 mJ. cm-2。
The hydrogen peroxide treatment group is to treat water containing algae cells and extracellular algal toxins by only adopting hydrogen peroxide and adding a certain amount of H2O2Solution makes two groups of H2O2The final concentrations of (A) were 0.4mM and 2 mM.
The intermittent combined treatment group is intermittent ultraviolet/H2O2Combination, H2O2The dose is controlled to be 0.025mM, and the total ultraviolet dose is 150mJ cm-2The first and second UV doses each comprise 50% of the total. In this example, H was added2O2When the concentration is 0.025mM, immediately turning on the ultraviolet quasi-parallel light beam instrument to perform the first ultraviolet irradiation with the dose of 75mJ cm-2Accounting for 50% of the total UV dose. After 10min, the ultraviolet quasi-parallel light beam instrument is opened again to perform the second ultraviolet irradiation with the dose of 75mJ cm-250% of the total UV dose. The observation period was set to 14d, 14d samples were taken and Na was added2S2O3The oxidizing agent is quenched for detection. Is provided withSet 3 parallel samples. The test results are shown in table 2.
TABLE 2
It can be seen from the test results in table 2 that the control effect on algal cells is not good and the degradation effect on extracellular algal toxins is limited only by using ultraviolet light or hydrogen peroxide, and the risk of increasing the content of extracellular algal toxins may be aggravated by the algal killing process instead. The intermittent combined method can excite strong oxidative free radicals OH in the algae cells to cause damage to important organelles such as nucleic acid, a photosynthetic system and the like in the algae cells, and attack the external structure of the algae cells with extracellular free radicals OH to form internal and external dual attack, thereby efficiently inactivating the algae cells and simultaneously degrading intracellular algae toxins. Inactivating algae cells by inducing intracellular free radical OH to form algae cell internal damage, and inactivating algae cells by inducing intracellular free radical OH to form algae cell internal damage, ultraviolet rays and H required by the algae cell internal damage2O2The dosage of the additive is lower, and the dosage is obviously reduced compared with the dosage used independently, and the cost is obviously reduced.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (35)
1. A method for treating algal bloom or red tide by intermittently combining ultraviolet rays and hydrogen peroxide comprises the following steps:
adding hydrogen peroxide into the water body suffering from algal bloom or red tide, and immediately performing primary ultraviolet source irradiation; wherein the water body contains algae cells and extracellular algal toxins;
and after the first-time ultraviolet source irradiation is finished, stopping the irradiation to enter an intermittent stage, wherein the time of the intermittent stage is 5-60 min, and then carrying out second-time ultraviolet source irradiation so as to realize the treatment of algal bloom or red tide.
2. The method of claim 1, wherein the total dose of the ultraviolet source radiation is 20-300 mJ-cm-2(ii) a The total dosage concentration of the hydrogen peroxide in the water body is 0.01-1 mmol/L.
3. The method of claim 2, wherein the first UV source irradiation is performed at a dose of 20% to 50% of the total dose of UV source irradiation; the dose for implementing the second time of ultraviolet source irradiation is 50% -80% of the total dose of ultraviolet source irradiation.
4. The method according to claim 1, wherein the time of the batch phase is 5-30 min.
5. The method of claim 1, wherein after the second uv irradiation, hydrogen peroxide is dosed into the water body and a third uv irradiation is performed.
6. The method of claim 5, wherein the third UV radiation is applied at a dose of 20-100 mJ-cm-2(ii) a The dosage concentration of the added hydrogen peroxide is 0.01-0.2 mmol/L based on the volume of the water body.
7. The method of any one of claims 1-6, wherein the body of water is an environmental body of water or water to be treated by a water treatment facility.
8. The method of any one of claims 1-6, wherein the body of water is an environmental body of water or water to be treated by a water treatment facility.
9. The method of claim 7, wherein the environmental water body comprises a lake, river, pond, reservoir water, or ocean.
10. The method of claim 8, wherein the environmental water body comprises a lake, river, pond, reservoir water, or ocean.
11. The method of any one of claims 1-6, wherein the algal cells are algae capable of forming a water bloom or red tide.
12. The method of claim 11, wherein the algal cells comprise one or more of cyanobacteria, green algae, diatoms, dinoflagellates, chrysophyceae, conidiophores, and dinoflagellates.
13. The method of any one of claims 1 to 6, wherein the extracellular algal toxin is an algal toxin capable of causing one or more symptoms of hepatotoxicity, respiratory paralysis, vomiting, diarrhea, nervousness and/or death in aquatic animals or humans.
14. The method of claim 13, wherein the algal toxin comprises one or a combination of two or more of a hepatotoxin, a neurotoxin, a diarrheal toxin, a memory deficit toxin, and a ciguatoxin.
15. The method of claim 14, wherein the hepatotoxin comprises one or a combination of two or more of microcystins, nodulotoxins, and cyromotoxins.
16. The method of claim 14, wherein the neurotoxin comprises one or a combination of two or more of anabaena toxin-a, saxitoxin, neosaxitoxin, gonyatoxin.
17. The method of claim 14, wherein the diarrheal toxin comprises a lipopolysaccharide endotoxin and/or a finotoxin.
18. The method of claim 14, wherein the memory-deficit toxin comprises domoic acid.
19. The method of any of claims 1-6, wherein the ultraviolet source comprises the sun, or a device or apparatus capable of generating ultraviolet light.
20. The method of claim 19, wherein the uv source is a uv source capable of providing C-band uv.
21. The method of claim 20, wherein the device or apparatus capable of generating ultraviolet light comprises one or a combination of two or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a diode, and an LED lamp.
22. The method of claim 7, wherein the ultraviolet source comprises the sun, or a device or apparatus capable of generating ultraviolet light.
23. The method of claim 22, wherein the uv source is a uv source capable of providing C-band uv.
24. The method of claim 23, wherein the device or apparatus capable of generating ultraviolet light comprises one or a combination of two or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a diode, and an LED lamp.
25. The method of any one of claims 1-6, wherein the UV source irradiation comprises irradiation outside the body of water and/or irradiation inside the body of water.
26. The method of claim 7, wherein the irradiating comprises irradiating outside the body of water and/or irradiating inside the body of water.
27. The method of claim 19, wherein the uv source irradiates comprises irradiating outside the body of water and/or irradiating inside the body of water.
28. The method according to any one of claims 1 to 6, wherein the manner of adding the hydrogen peroxide comprises adding the hydrogen peroxide directly or adding a chemical substance capable of generating the hydrogen peroxide.
29. The method of claim 28, wherein the chemical capable of generating hydrogen peroxide is one or a combination of two or more of ionization, hydrolysis, and oxidation to generate hydrogen peroxide.
30. The method of claim 7, wherein the manner of adding the hydrogen peroxide comprises adding the hydrogen peroxide directly or adding a chemical capable of generating hydrogen peroxide.
31. The method of claim 30, wherein the chemical capable of generating hydrogen peroxide is one or a combination of two or more of ionization, hydrolysis, and oxidation to generate hydrogen peroxide.
32. The method of claim 19, wherein the manner of adding the hydrogen peroxide comprises adding the hydrogen peroxide directly or adding a chemical capable of generating hydrogen peroxide.
33. The method of claim 32, wherein the chemical capable of generating hydrogen peroxide is one or a combination of two or more of ionization, hydrolysis, and oxidation to generate hydrogen peroxide.
34. The method of claim 25, wherein the manner of adding the hydrogen peroxide comprises adding the hydrogen peroxide directly or adding a chemical capable of generating hydrogen peroxide.
35. The method of claim 34, wherein the chemical capable of generating hydrogen peroxide is one or a combination of two or more of ionization, hydrolysis, and oxidation to generate hydrogen peroxide.
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| JPS62262792A (en) * | 1986-05-09 | 1987-11-14 | Iwasaki Electric Co Ltd | Treatment of organic material-containing water |
| CN106915798A (en) * | 2017-03-09 | 2017-07-04 | 复旦大学 | A kind of method of the pre-oxidation enhanced coagulation efficient algae removal of green non-pollution |
| CN107162098A (en) * | 2017-06-12 | 2017-09-15 | 北京建筑大学 | The minimizing technology and its processing unit of Anabaena spiroides in water |
| CN109896583A (en) * | 2019-03-06 | 2019-06-18 | 深圳市深水龙岗水务集团有限公司 | A kind of high-strength ultraviolet light-hydrogen peroxide removes the device of algae toxin in water body |
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| JPS62262792A (en) * | 1986-05-09 | 1987-11-14 | Iwasaki Electric Co Ltd | Treatment of organic material-containing water |
| CN106915798A (en) * | 2017-03-09 | 2017-07-04 | 复旦大学 | A kind of method of the pre-oxidation enhanced coagulation efficient algae removal of green non-pollution |
| CN107162098A (en) * | 2017-06-12 | 2017-09-15 | 北京建筑大学 | The minimizing technology and its processing unit of Anabaena spiroides in water |
| CN109896583A (en) * | 2019-03-06 | 2019-06-18 | 深圳市深水龙岗水务集团有限公司 | A kind of high-strength ultraviolet light-hydrogen peroxide removes the device of algae toxin in water body |
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