CN102765775A - Sewage treatment method by ultrasonic wave enhanced diatomite - Google Patents
Sewage treatment method by ultrasonic wave enhanced diatomite Download PDFInfo
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- CN102765775A CN102765775A CN2012102030568A CN201210203056A CN102765775A CN 102765775 A CN102765775 A CN 102765775A CN 2012102030568 A CN2012102030568 A CN 2012102030568A CN 201210203056 A CN201210203056 A CN 201210203056A CN 102765775 A CN102765775 A CN 102765775A
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- sewage
- zeyssatite
- ultrasonic
- ultrasonic wave
- diatomite
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Abstract
The invention aims to provide a sewage treatment method by ultrasonic wave enhanced diatomite. The method is as below: storing sewage in a sewage unit; pouring diatomite subjected to refining treatment or modified diatomite into the sewage unit; moving the diatomite in the unit through an ultrasonic process; discharging precipitates through a mud discharge pipe after precipitation; and discharging a treated supernatant through a discharge pipe, so as to achieve standard discharge. The ultrasonic processor has an ultrasonic frequency of 10-1000kHz, power of 20-1000W, an ultrasonic interval time of 0.5-10 days, and a treatment time of 0.5-30min for each time. According to the invention, metal oxides in the diatomite or modified diatomite catalyze decomposition of hydrogen peroxide formed in an ultrasonic cavitation process, under strengthening effect of the ultrasonic wave, to produce hydroxyl radicals with higher chemical reactivity. The method has obvious removal effect on a variety of pollutants in the ship sewage.
Description
Technical field
What the present invention relates to is a kind of sewage water treatment method.
Background technology
Along with development of global economy, marine traffic capacity has also obtained the growth of advancing by leaps and bounds, and the most trade of goods in the whole world is accomplished through sea transport.The sewage that these boats and ships ride the sea and produce in the process, if without the just directly discharging of certain treatment measures, can be to the healthy generation huge threat of ocean environment with the mankind.Face the pollution situation that increasingly serious vessel sewage causes; International Maritime Organizaton (IMO) has formulated International Convention for the Prevention of Pollution from Ships-" MARPOL73/78 "; Carried out many regulations for preventing and treating the vessel sewage pollution in the supplemental provisions IV of pact, come into force on September 27th, 2003.The sewage that boats and ships produce is mainly and comprises Sewage from Ships (Heisui River), buck, boats and ships oily water and ballast water for ship.According to the definition of pact supplemental provisions VI, Sewage from Ships mainly is meant: the lavatory of any pattern and the ejecta of urinal and other wastes; The ejecta of hand washing sink, wash tub and these place water vents in consulting room (pharmacy, ward etc.); The ejecta in the animal place that lives is housed; Be mixed with other waste water of the ejecta of above-mentioned definition, Sewage from Ships also often is called " Heisui River "; And buck is meant other sewage that produce on the ship except that Heisui River, mainly is waste water and the refuse of locating from kitchen, laundry and washroom etc.; The boats and ships oily water mainly comprises oily ballast, oil-containing washwater and the engine room water that produces in the boats and ships course of normal operation; Water ballast is stability and the buoyancy that is used for regulating boats and ships; Contain unicellular lower eukaryotes such as plant plankton, zooplankton, bacterium and pathogenic agent and some fish or the like in the water ballast, the principle of ballast water treatment is the propagation that prevents, reduces and finally eliminate unwanted aquatic organism and pathogenic agent.
The Sewage from Ships that requirements of convention is handled mainly is " Heisui River ".Though " buck " to dischargings such as washing, kitchen and laundry institutes do not provide processing requirements, when and must handle during " Heisui River " dual disposal.In addition, some countries and regions are the local water environment quality of protection, have formulated strict more Sewage from Ships emission standard alone, such as the BOD of IMO requirement
5, SS and colibacillary discharge index are respectively 50mg/L, 50mg/L and 250/100mL, and the discharge index of marine site, U.S. Alaska laws and regulations requirement is respectively 20mg/L, 25mg/L and 100/100mL.And some area requires Heisui River and buck all will handle; Even forbid discharging any type of Sewage from Ships at some special and responsive water bodys, such as wilderness area, waterhead area and rare fish habitat etc.And require in the water ballast of discharging for ballast water for ship, minimum size is more than or equal to 50 microns organism, and minimum size is more than or equal to 10 microns but less than 50 microns organism in every milliliter, and every cube of can survive is less than 10.The discharging of target microorganism should not surpass the concentration of stipulating.According to the human beings'health standard, target microorganism should include but not limited to: every 100mL contains less than the poisonous vibrio cholerae of 1cfu (colony-forming unit) or every gram (weight in wet base) and contains less than 1cfu zooplankton sample.Every 100mL contains the intestinal bacteria that are less than 250cfu.Every 100mL contains the enterococcus bacteria that is less than 100cfu.
At present mainly take two kinds of ways for the processing of vessel sewage, on-the-spot disposal discharges and through on boats and ships, storing, waits to be carried to the land and focus on the ship.Domestic at the harbour or the harbour technology that sewage work adopted on the bank be mainly biological contact oxidation process and oxidation ditch.With respect in the on-the-spot disposal technology on the ship for the degree that requires of the space of boats and ships and treatment technology; Sewage from Ships is collected in the process of ship running and stored; Be transported to the method that harbour or harbour sewage work on the bank handles; To hang down for the requirement on the ship's repairs & maintenance facilities, the device that only is to use some can store Sewage from Ships, and investment cost is lower.But these storage facilities but can take the effective capacity in the boats and ships, and because the unstable of the Sewage from Ships water yield confirms also to have great difficulty for the volume of storage facility.Also special sewage receiving equipment need be set at the harbour in addition, increase the manpower and materials expense and consume more times.And the discharging of the on-the-spot disposal of Sewage from Ships, effective capacity space of not only having practiced thrift boats and ships, and also treated sewage can not pollute in the discharging of any waters.The method of studying several types of sewage in the more processing boats and ships at present both at home and abroad mainly contains mechanical process, physics method, chemical process and biological process.These methods find to exist energy consumption in research process bigger, and there is certain problem in the low and more high shortcoming of cost of efficient in reality is promoted.
Ultrasonic technology is a kind of novel environmental technology that development in recent years is got up.Have operation and control easily, and advantage such as reaction conditions is gentle, and speed of response is fast.Can unite use separately or with other water technologies, be a kind of water technology that development potentiality and application prospect are arranged very much.In the aqueous solution, the main influence that produces when cavitation takes place has: thermolysis, free radical reaction and chemical conversion, supercritical water oxidation.This is just for being difficult to realize that those reactions that maybe can not realize provide a kind of new very special materialization environment under general chemical reaction condition.Although use the UW a series of pollutents in the water body of can degrading simply, easily separately, should technology still there be problems such as degradation efficiency is low, long reaction time, energy consumption height, improve its reaction efficiency greatly with other technologies coupling meeting.
Zeyssatite is after ancient times, unicellular lower plant diatom remains were piled up; What form through Diagn under certain geologic condition a kind ofly has a porous biogenic sediment rock; Be by the dead later remains formation of deposits of diatom; The essential mineral composition is pearl opal and mutation thereof, and chemical ingredients mainly is SiO
2, and contain a spot of Al
2O
3, Fe
2O
3, CaO, Na
2O, MgO etc. and impurity such as organic matter.Zeyssatite is because its chemical property is stable, high adsorption capacity, and strainability is good, is insoluble to any strong acid, in wastewater treatment, is widely used.Diatomaceous WWT mechanism is absorption, coagulation and neutralization synergy.Because diatomite has huge specific surface area and powerful surface adsorption performance, take off steady colloid and very easily be adsorbed on the zeyssatite, and adhered between the diatomite particle of pollution substance very big mutual adsorptive power is also arranged.So after joining in the waste water as coagulating agent modification infusorial earth; Can form granularity and all bigger flco of density fast, and the good stability of this flco, even after flco is broken; Also reflocculation can take place, this is that other waste water conditioner commonly used such as aluminium salt, molysite is incomparable.Utilize the coagulation and the characterization of adsorption of the uniqueness that zeyssatite has; In addition also owing to also have a large amount of MOXs in its moity; Therefore utilize ultrasound-enhanced diatomaceous effect, can strengthen the synergy between the two greatly, improve treatment effect for vessel sewage and other polluted water; Make that it can qualified discharge, reduce harm ocean environment.
The patent of application number 200410098588.5 provides utilizes ultrasonic fortified flocculation to remove the method for algae in the water body, adopts ultrasound-enhanced flocculant of polymeric aluminium chloride to carry out coagulation, removes algae then.Patent No. ZL200310117710.4 provides a kind of method of removing algae in the former water of water factory with UW fast; Coagulating agent is added in the former water in the coagulation reaction tank; Carry out coagulating, in the former water under the UW that simultaneously ultrasonic equipment is produced directly puts on through transverter.These two kinds of effects that method all is ultrasound-enhanced common coagulants.
Summary of the invention
The method that the object of the present invention is to provide the intensified by ultrasonic wave zeyssatite of harmful organisms such as the organic pollutant handled in the vessel sewage, oils, algae, pathogenic agent, suspended substance to dispose of sewage.
The objective of the invention is to realize like this:
The method that intensified by ultrasonic wave zeyssatite of the present invention is disposed of sewage; It is characterized in that: sewage is stored in the sewage device, and the zeyssatite or the zeyssatite after the modification that will pass through after the process of refinement are poured in the sewage device, moves in sewage device through the mobile ultrasonic treater; Through deposition; Throw out is discharged through the spoil disposal pipeline, and the supernatant after the processing is discharged through vent pipe, realizes qualified discharge; The ultrasonic frequency of described processor for ultrasonic wave is that 10～1000kHz, power are 20～1000w, and UW pitch time is 0.5～10 day, and each treatment time is 0.5～30min.
The present invention can also comprise:
1, described diatomaceous process of refinement process is with the diatomite original soil drying, pulverizes, grinds, dries and screening, wherein selects 100～200 mesh sieves to sieve.
2, described diatomaceous modification treating processes is to use sulfuric acid, hydrochloric acid, sodium hydroxide to embathe, and uses whisking appliance to stir, then heat drying.
3, described diatomaceous modification treating processes is that described MOX comprises TiO at zeyssatite area load MOX
2, CuO, MnO
2, Fe
3O
4Or oxyhydroxide.
4, with adding aluminium system, ferric flocculant or macromolecule organic flocculating agent, zeolite, clay, wilkinite, graphite in zeyssatite after the process process of refinement or the zeyssatite after the modification.
Advantage of the present invention is: the present invention is under hyperacoustic strengthening effect, and diatomaceous absorption and coagulation effect will be greatly improved.Simultaneously; The decomposition of the hydrogen peroxide that the MOX in the zeyssatite after zeyssatite or the modification also can catalysis ultrasonic cavitation process forms; Generation has the hydroxyl radical free radical of higher chemical reactivity, all will have tangible removal effect for all contaminations in the vessel sewage.Synergy between UW and the zeyssatite, the novel method that makes this intensified by ultrasonic wave zeyssatite handle vessel sewage will have broad application prospects.Simultaneously, this technology also is applicable to the treating processes of other polluted water.
Embodiment
In the face of doing in more detail, the present invention describes down:
Hyperacoustic heating mechanism, mechanical schemes, cavitation mechanism produces radical and chemical conversion.These several kinds of UW mechanism of action interact, and interact, and in the UW water treatment procedure, play an important role.The cavitation effect that UW produces; Can produce a large amount of micro-bubbles; These micro-bubbles form, vibrate, grow, are contracted in the process of collapse this extreme physical environment at it possibly cause some particular chemical reaction; Can form powerful bursting force, can the emulsion micelle in the oil-containing water broken and realizes breakdown of emulsion.Harmful organisms such as the radical that cavitation processes produces also can be for the organic pollutant in the vessel sewage, algae and pathogenic agent have the effect of better degraded removal and deactivation.
The coagulation of the uniqueness that zeyssatite has and characterization of adsorption.Adsorptive power that zeyssatite is very strong and very big loading capacity are because its diatom shell has micropore a large amount of, ordered arrangement, thereby make zeyssatite have very big specific surface area.And coagulation can further be strengthened adsorption.Zeyssatite is carried out modification zeyssatite afterwards have higher adsorptive power and better coagulation effect, make it form bigger and more closely knit flco, and flco has satisfactory stability property with pollutent; And the zeyssatite after the modification will have huge specific surface area and powerful surface adsorption performance, and pore structure improves, and takes off steady colloid and very easily is adsorbed on the zeyssatite.Also can in diatomite, add other an amount of coagulating agent, form composite coagulant, like aluminium system or ferric flocculant, or macromolecule organic flocculating agent.Diatomite particle can be used as the skeleton that forms flco, improves the structure of alumen ustum, has certain effect of coagulating that helps, and the flco that makes formation is closely knit and settling property preferably arranged.In addition, after the activated sour modification of zeyssatite was handled, its specific surface area increased greatly, generates the solubility salt behind the oxide compound of the iron in the zeyssatite, aluminium, calcium etc. and the acid-respons, in water, can hydrolysis form the very strong polymkeric substance of coagulation.
Under hyperacoustic strengthening effect, can make diatomaceous coagulation and absorption absorption to be greatly enhanced.Apply UW, organic thermal motion quickening in the vessel sewage, specific surface area are improved, the speed that organic constituent and zeyssatite collision form co-precipitation improves, thus the enhanced coagulation effect.UW can utilize its dissemination to increase diatomaceous specific surface area, has improved diatomaceous adsorption, thus the enhanced coagulation effect.When ultrasonic frequency was higher, the mechanical effect that UW also capable of using produces to clean fast and effectively the zeyssatite surface, and impurity in the removing zeyssatite and the impurity in the zeyssatite space, made it can accomplish regenerative process rapidly, improved adsorption effect.In addition, the ultrasonic procedure cavitation H that can generate
2O
2, owing to promptly contain Al in the natural zeyssatite
2O
3, Fe
2O
3, MOXs such as CaO, MgO, under action of ultrasonic waves, these MOXs can catalysis H
2O
2Decomposition, produce and to have hydroxyl radical free radical than the extensive chemical oxidation activity, all have good effect of removing for all contaminations in the vessel sewage.If at zeyssatite area load MOX, like TiO
2, CuO, MnO
2, Fe
3O
4With oxyhydroxide or the like, the decomposition course of the hydrogen peroxide that the MOX of these loads equally can the catalysis ultrasonic cavitation produces down improves treatment effect.
Embodiment 1:
Sewage from Ships and oily(waste)water are collected through collection device respectively, and water ballast is stored in the ballast tank, according to different sewage volumes; Different quantities is poured in the sewage device through zeyssatite or the zeyssatite after the modification after the process of refinement, is moved in sewage device through the mobile ultrasonic treater then, in the process that moves with the organic pollutant in the sewage; Oils; Harmful organisms such as algae, pathogenic agent, suspended substance or the like is located to remove; Through the deposition of certain hour, throw out is discharged through the spoil disposal pipeline.Supernatant after the processing is discharged through vent pipe, realizes qualified discharge.Frequency of ultrasonic is 10～1000kHz, and hyperacoustic power is 20～1000w, and the treatment time is 0.5～30min, pitch time be the ultrasonic operation of 0.5～10d once.High frequency can be used for the impurity of zeyssatite and the impurity in zeyssatite surface and the space, realizes diatomaceous use repeatedly, reduces processing cost.
Embodiment 2: according to the working method of embodiment one, zeyssatite is carried out process of refinement, the process that becomes more meticulous mainly be with diatomite original soil through dry, pulverize, grind, oven dry and screening according to different quality, are selected 100～200 mesh sieves.
Embodiment 3: according to the working method of embodiment one, zeyssatite is carried out modification handle, adopt acid or alkali cleaning mode, use sulfuric acid, hydrochloric acid and sodium hydroxide to embathe, and use whisking appliance to stir, then heat drying.
Embodiment 4:, zeyssatite is carried out modification handle, at zeyssatite area load MOX, like TiO according to the working method of embodiment one
2, CuO, MnO
2, Fe
3O
4Or oxyhydroxide or the like.
Embodiment 5: according to the working method of embodiment one, in diatomite, add other an amount of coagulating agent, form composite coagulant, like aluminium system or ferric flocculant, or macromolecule organic flocculating agent.Perhaps the combination of zeyssatite and other non-metallic mineralss is used, and comprises zeolite, clay, wilkinite and graphite etc.Through obtaining the zeyssatite composite water disposal agent with upper type.
Claims (5)
1. the intensified by ultrasonic wave zeyssatite method of disposing of sewage; It is characterized in that: sewage is stored in the sewage device, and the zeyssatite or the zeyssatite after the modification that will pass through after the process of refinement are poured in the sewage device, moves in sewage device through the mobile ultrasonic treater; Through deposition; Throw out is discharged through the spoil disposal pipeline, and the supernatant after the processing is discharged through vent pipe, realizes qualified discharge; The ultrasonic frequency of described processor for ultrasonic wave is that 10～1000kHz, power are 20～1000w, and UW pitch time is 0.5～10 day, and each treatment time is 0.5～30min.
2. the method that intensified by ultrasonic wave zeyssatite according to claim 1 is disposed of sewage; It is characterized in that: described diatomaceous process of refinement process is with the diatomite original soil drying, pulverizes, grinds, dries and screening, wherein selects 100～200 mesh sieves to sieve.
3. the method that intensified by ultrasonic wave zeyssatite according to claim 1 is disposed of sewage is characterized in that: described diatomaceous modification treating processes is to use sulfuric acid, hydrochloric acid, sodium hydroxide to embathe, and uses whisking appliance to stir, then heat drying.
4. the method that intensified by ultrasonic wave zeyssatite according to claim 1 is disposed of sewage is characterized in that: described diatomaceous modification treating processes is that described MOX comprises TiO at zeyssatite area load MOX
2, CuO, MnO
2, Fe
3O
4Or oxyhydroxide.
5. the method for disposing of sewage according to the arbitrary described intensified by ultrasonic wave zeyssatite of claim 1-4; It is characterized in that: with adding aluminium system, ferric flocculant or macromolecule organic flocculating agent, zeolite in zeyssatite after the process process of refinement or the zeyssatite after the modification; Clay, wilkinite, graphite.
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Cited By (7)
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| CN102949979A (en) * | 2012-11-14 | 2013-03-06 | 南京工业大学 | Process for modifying diatomite |
| CN103214149A (en) * | 2013-04-27 | 2013-07-24 | 浙江中一检测研究院股份有限公司 | Advanced treatment method of high-concentration industrial wastewater |
| CN103771557A (en) * | 2014-01-24 | 2014-05-07 | 华北水利水电大学 | Method for removing pollutants in water by ultrasonic-absorption synergy |
| CN104563056A (en) * | 2013-10-23 | 2015-04-29 | 宋在洪 | Removal method of marine sediments using micro-air bubbles |
| CN104826579A (en) * | 2015-03-18 | 2015-08-12 | 深圳职业技术学院 | Magnetic kieselguhr adsorbent, preparation method and application thereof |
| CN108128867A (en) * | 2017-12-28 | 2018-06-08 | 中国科学院海洋研究所 | A kind of supersonic modifying method for improving clay and administering harmful algal bloom efficiency |
| WO2020010678A1 (en) * | 2018-07-10 | 2020-01-16 | 中冶华天南京工程技术有限公司 | Novel material for in-situ decontamination of turbid river water and preparation method thereof |
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| CN108128867B (en) * | 2017-12-28 | 2021-04-27 | 中国科学院海洋研究所 | Ultrasonic modification method for improving efficiency of clay in treatment of harmful algal blooms |
| WO2020010678A1 (en) * | 2018-07-10 | 2020-01-16 | 中冶华天南京工程技术有限公司 | Novel material for in-situ decontamination of turbid river water and preparation method thereof |
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Application publication date: 20121107 |