CN103771557A - Method for removing pollutants in water by ultrasonic-absorption synergy - Google Patents
Method for removing pollutants in water by ultrasonic-absorption synergy Download PDFInfo
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- CN103771557A CN103771557A CN201410033388.5A CN201410033388A CN103771557A CN 103771557 A CN103771557 A CN 103771557A CN 201410033388 A CN201410033388 A CN 201410033388A CN 103771557 A CN103771557 A CN 103771557A
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Abstract
The invention relates to a method for removing pollutants in water by ultrasonic-absorption synergy and aims at realizing fast and high-efficiency removal of the pollutants in the water. The method is characterized in that a special absorbing agent (such as diatomite and coal ash) is added in the process of carrying out ultrasonic treatment on the water to be treated so as to be effectively dispersed in the ultrasonic process and enhance the occurrence of the absorption process; simultaneously, due to enrichment of the pollutants on the absorbing agent and the catalytic action of the absorbing agent, the absorption process can intensify the ultrasonic-removing action, so that the synergistic action is generated. In the method, the pollutants in the water are removed by the synergistic action of ultrasonic radiation and the absorbing agent, the needed ultrasonic-radiation energy is lower, the total energy consumption is lower, and the solid absorbing agent is easily and fast removed by the processes of precipitation, filtering and flocculation and the like. By adoption of the method, fast removal of organic pollutants and heavy metals, sterilization and disinfection can be realized; and the method also can be used for treating feed water, and if the diatomite is adopted as the absorbing agent, aromatic pollutants and humic acid such as pesticide and surface active agents in the water can be effectively removed.
Description
Technical field
The present invention relates to field of water processing technology, be specifically related to a kind of ultrasonic and collaborative method of removing water pollutant of sorbent material.
Background technology
Ultrasonic wave refers to the higher elastic wave of range of frequency that frequency ratio people ear can be heard.Ultrasonic wavelength in liquid is 0.015～10 cm (being equivalent to 15 kHz to 10 MHz), is far longer than the size of molecule, and therefore ultrasonic wave is not direct acoustic wave action to organic removal.Ultrasonic wave is propagated to surrounding by liquid medium, and in the time that acoustic energy is enough high, within the loose semi-period, the intermolecular magnetism of liquid phase is broken, and forms cavitation nucleus.When bubble-break, around bubble, short space forms hot localised points, produce high temperature (5000 K), high pressure (50 Mpa), and produce the microjet with intense impact power of speed approximately 110 m/s, and in liquid with powerful shockwave.Because cavitation bubble collapses the powerful hydromeehanics shearing force while going out, can make the carbon bond in larger molecular organics carbochain rupture, be accompanied by high mars free radical (H, OH, HO
2) generation, specifically see formula (1)-(4).These conditions are enough to make organism that chemical bond rupture, water burning, pyrolytic decomposition or free radical reaction occur in cavitation bubble, for an extreme physical environment has been created in organic removal.
H
2O →?H·?+?HO· (1)
H·?+?O
2?→?·HO
2?→?HO·?+?1/2O
2 (2)
O
2?→?2·O (3)
·O?+?H
2O?→?2HO· (4)
But ultrasonic wave is on the basis based on highly energy-consuming to organic removal and removal, and removal efficiency is limited, therefore occur that ultrasonic technique and other removal process are as the combined utilization of photochemical catalysis, hydrogen peroxide oxidation, Fenton oxidation, ozone oxidation, electrochemical techniques.The oxygenants such as ultrasonic and hydrogen peroxide, Fenton reagent and ozone are combined while use, because ultrasonic energy consumption itself is higher, add the expense of oxidising agent, cause overall high cost, are unfavorable for practical application.Remove in the process of pollutent thing at ultrasonically catalyzing, for multiselect, titanium dioxide, zinc oxide etc. possess the oxide compound of photocatalytic activity, although can realize the quick removal (Wang Ying of chlorophenol, dyestuff, agricultural chemicals and heterocyclic organic pollutant, Niu Junfeng, Zhang Zhe, Long Xingxing. organic pollutants is removed in ultrasonic-photochemical catalysis. chemical progress, 2008,20 (10): 1621-1627), but in actual water treatment procedure, these nano-scale photocatalysts that may use not only price higher, be difficult to reclaim and reuse, but also may destroy water ecology.
Adsorption technology is one of water technology of having carried out up to now broad research and application, pollutent directly out and not can be caused to follow-up pollution from liquid phase sharp separation.The typical pollutant such as organic pollutant and heavy metal can be by Adsorption from water quickly and efficiently, and therefore adsorption process is thought the water technology of tool actual application value by Environmental Protection Agency.But because the difference of sorbent material character causes the efficiency of Adsorption pollutent still barely satisfactory, and these sorbent material costs used are higher, are difficult to popularize.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of less energy-consumption, ultrasonic absorbing synergic is removed the method for water pollutant cheaply, the method realizes the ultrasonic and integrated application of adsorption technology in water treatment, processing efficiency is stable, reliable, can be applicable to wider waste water ph scope, for the function that the biological pollutants such as organic pollutants, inorganic pollutant and bacterium, virus all have fast, efficiently remove and kill that mainly contains in water, and then realize the high-efficient purification of water quality.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
In pending water is carried out to supersound process process, add specific sorbent material (as diatomite, flyash etc.), this class sorbent material can effectively be disperseed in ultrasonic irradiation process, promotes the generation of adsorption process; Due to the enrichment of pollutent on sorbent material and the katalysis of sorbent material, adsorption process can be strengthened ultrasonic removal effect simultaneously, thereby the synergy of generation realizes the integrated application of ultrasonic technique and adsorption technology.Concrete grammar is as follows:
In pending water, add sorbent material, simultaneously with 20～1000 kHz, the sound intensity 0.2～10 W/cm
2 ultrasonic irradiation 5～120 min, described sorbent material is containing at least one in flyash, diatomite.Handled waste water, sewage or water source current operation scheme or employing are dynamic, or adopt static.
Preferred ultrasonic frequency scope is that 30～300 kHz, the sound intensity are 0.3～6W/cm
2.
For different water quality and running cost, only need the suitable ultrasonic frequency of adjustment in above parameter area
,power and sorbent material just can be realized the efficient ultrasonic absorbing synergic of pollutent and remove.
The solid-to-liquid ratio of described sorbent material and treatment sewage is 0.1～200 mg:20mL.
For different water quality and running cost, only need the suitable ultrasonic frequency of adjustment in above parameter area
,power and sorbent material (suitable kind and consumption) just can be realized the efficient ultrasonic absorbing synergic of pollutent and remove.
By weight percentage, also contain at least one in tourmalinite, medical stone in described sorbent material, its addition reaches 1～100 mg/L with the content in pending water and is as the criterion.
The granularity of described flyash is 1500～50 orders.
Described diatomaceous granularity is 1500～50 orders.
The method that the regeneration method of described sorbent material can adopt traditional sorbent material generally to adopt, as regeneration under alkaline condition, high temperature oxidation are regenerated and add the ordinary methods such as oxygenant regeneration.
In pending water source, add after sorbent material diatomite
,do not need regulator solution pH value can carry out ultrasonic irradiation processing
.
In treatment sewage, add after adsorbent powder coal ash, carry out again ultrasonic irradiation processing after can regulating its pH to 5～9, to strengthen scrubbing effect.
The present invention has actively useful effect:
1. in the inventive method, ultrasonic radiation and sorbent material synergy are removed water pollutant, and required ultrasonic radiation energy is lower, energy consumption is totally less, and solid adsorbent is easy to remove fast by processes such as precipitation, filtration, flocculations.
2. ultrasonic planar water treating processes of the present invention can be used separately, also can combine with other unit for treating water operation, realizes optimum water treatment effect; The inventive method is not only applicable to the water conditioning of water in enormous quantities, is applicable to purification of water quality and the lifting of less generation and usage quantity yet, as medical waste water etc.
3. involved in the present invention can produce with ultrasonic radiation the solid waste such as the mineral such as synergistic diatomite, and flyash, (if flyash itself is exactly waste recycling) cheap and easy to get, purify with low cost; The object that can realize " treatment of wastes with processes of wastes against one another " for this collaborative processes processing waste water, has potential economic worth.It is upper that these used sorbing materials can be used in material of construction processing, can not produce ultimate disposal problem.
4. the inventive method can be used for the processing of waste water or sewage (including the biological pollution such as organic pollutants, heavy metal, radionuclide and bacterium and virus), as adopt flyash, diatomite etc. as sorbent material, can realize the quick removal of organic pollutant, also can realize the Adsorption of heavy metal; Also processing that can water supply, is sorbent material as adopted diatomite, can effectively remove the aromatics such as agricultural chemicals, tensio-active agent pollutent and humic acids in water, effectively guarantees water quality safety; If add the natural mineral such as tourmalinite, medical stone in sorbent material, just can in water, add the nutritive element useful to human body, significantly increase water quality.
Accompanying drawing explanation
Fig. 1 is Acid Orange II ultraviolet-visible spectrum trend map over time in the collaborative removal of ultrasonic wave-flyash azoic dyestuff Acid Orange II process;
Fig. 2 is the collaborative first order kinetics mimic diagram of removing Acid Orange II process of independent ultrasonic removal, separately Powder ash adsorption and ultrasonic wave-flyash;
Fig. 3 is the collaborative clearance trend map of removing azoic dyestuff Acid Orange II of ultrasonic wave-flyash under differential responses pH condition;
Fig. 4 is the collaborative methylene blue clearance trend map of removing of ultrasonic wave-diatomite under differential responses pH condition;
Fig. 5 is the collaborative methylene blue clearance trend map of removing of ultrasonic wave-diatomite under different diatomite dosage conditions;
After the cyclic regeneration of Fig. 6 flyash, work in coordination with for ultrasonic wave-flyash the clearance trend map of removing azoic dyestuff Acid Orange II.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
The collaborative azoic dyestuff Acid Orange II of removing in water of embodiment 1 ultrasonic wave-flyash
Get and contain azoic dyestuff Acid Orange II (anionic dyestuff, concentration is 10 mg/L) 400 mL add in 500 mL Erlenmeyer flasks as simulated wastewater, after adding wherein 3g flyash (crossing 200 mesh sieves), shake up, be positioned over ultrasonic cleaner (AS3120A, Tianjin Ao Tesai Instrument Ltd.) in, take frequency as 40 KHz, power processes 60 min as the ultrasonic irradiation of 100 W.Fig. 1 is the variation that the uv-visible absorption spectra of Acid Orange II in ultrasonic-flyash combination treatment process occurs in time, and as known in the figure, ultrasonic-flyash combination treatment can realize the quick removal of this dyestuff; And separately when supersound process the each absorption peak of Acid Orange II change slowly, show that its removal effect is not obvious; Fig. 2 is the first order kinetics mimic diagram of independent ultrasonic removal, separately Powder ash adsorption and the collaborative removal process of ultrasonic flyash, and the first order kinetics rate constant of independent ultrasonic removal as seen from the figure, separately Powder ash adsorption and the collaborative removal process of ultrasonic flyash reaches respectively 7.55 × 10
-4min
-1, 0.0107 min
-1and 0.0246 min
-1.The first order kinetics rate constant of the collaborative removal process of ultrasonic flyash is 2.15 times of other two kinds of process rate constants, and this illustrates that the two has produced obvious synergy.Using diatomite as sorbent material, test shows can produce equally ultrasonic absorbing synergic effect; And diatomite in use can not produce secondary pollution, can be used for to water treatment.Test-results also shows, is sorbing material if select titanium dioxide, kaolin etc., can not produce synergy with supersound process, is unfavorable for realizing the integrated application of two kinds of technology.
Azoic dyestuff Acid Orange II in the collaborative removal of ultrasonic wave-flyash water under embodiment 2 condition of different pH
Getting a series of 400 mL Acid Orange IIs (10 mg/L) simulated wastewater adds respectively in 500 different mL Erlenmeyer flasks, after adding wherein again 3g flyash (crossing 200 mesh sieves), shake up, regulate respectively the extremely different pH value of solution in each Erlenmeyer flask, be placed on respectively again in ultrasonic cleaner, take frequency as 50 KHz, power is 100 W ultrasonic wave, carry out irradiation associated treatment 60 min, pollutants removal rate under each pH condition is referring to Fig. 3, as seen from the figure, even the pH condition difference of each reaction system, within the scope of wider pH value, still can realize the quick removal of Acid Orange II, this shows that in ultrasonic wave-flyash associated treatment process, processing efficiency is stable, reliably, the method can be applicable to wider pending water pH value scope.
The collaborative water Methylene Blue of removing of embodiment 3 ultrasonic wave-diatomite
Get 400 mL methylene blues (cationic dyestuff, 10 mg/L) simulated wastewater and add in 500 mL Erlenmeyer flasks, ultrasonic frequency is that 60 KHz, power are 100 W.When Fig. 4 has investigated diatomite (cross 50 mesh sieves) dosage and has been 25 mg under differential responses pH condition the clearance to methylene blue, show that clearance is higher under alkaline condition, and minimum under acidic conditions; Fig. 5 investigated different diatomite dosages on methylene blue clearance impact, show to improve diatomite dosage can by methylene blue almost completely remove.
Contain Cu to 200 mL
2+concentration is to add 3 g flyash in the simulated sewage of 10 mg/L, then take frequency as 100 KHz, power processes 10 min as the ultrasonic irradiation of 100 W, and leaves standstill 120 min, the after testing Cu in this simulated sewage
2+concentration is reduced to 0.56 mg/L.Concurrent control test: do not apply ultrasonic radiation after adding flyash, only promote adsorption equilibrium by magnetic stirrer, Cu
2+concentration is at most only reduced to 1.30 mg/L.
Contain in colibacillary simulated sewage and add after 3g flyash to 400 mL, then take frequency as 40 KHz, power processes 60 min as the ultrasonic irradiation of 100 W, assay shows, the inventive method reaches 96.7% to colibacillary killing rate.Concurrent control is tested and is shown, if only apply ultrasonic radiation, colibacillary killing rate at most only reaches 34.2%.
To in embodiment 1, embathe 60 min with the flyash of crossing with the diluted sodium hydroxide solution of 2 mol/L, then use through deionized water and be washed till condition of neutral pH, after dry in baking oven, remove Acid Orange II for the ultrasonic absorbing synergic of next batch, concrete reaction conditions is with embodiment 1.When test-results (referring to Fig. 6) shows that the flyash of regeneration is removed Acid Orange II for ultrasonic absorbing synergic, there is not obvious reduction in the removal efficiency of Acid Orange II.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (7)
1. ultrasonic absorbing synergic is removed a method for water pollutant, it is characterized in that, in staying water, adds sorbent material, simultaneously with frequency 20～1000 kHz, the sound intensity 0.2～10 W/cm
2ultrasonic irradiation 5～120 min, described sorbent material is containing at least one in flyash, diatomite.
2. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, described hyperacoustic range of frequency is that 30～300 kHz, the sound intensity are 0.3～6 W/cm
2.
3. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, the solid-to-liquid ratio of described sorbent material and treatment sewage is 0.1～200 mg:20 mL.
4. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, by weight percentage, also contain at least one in tourmalinite, medical stone in described sorbent material, its addition reaches 1～100 mg/L with the content in staying water and is as the criterion.
5. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, the granularity of described flyash is 1500～50 orders.
6. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, described diatomaceous granularity is 1500～50 orders.
7. ultrasonic absorbing synergic according to claim 1 is removed the method for water pollutant, it is characterized in that, renovation process after described sorbent material uses: will soak 0.5～48 h with the diluted sodium hydroxide solution that the absorption of crossing has the sorbent material of pollutent to be placed in 0.1～5 mol/L, be washed till condition of neutral pH with deionized water again, dry rear with for subsequent use.
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Cited By (9)
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|---|---|---|---|---|
| CN104528911A (en) * | 2014-12-02 | 2015-04-22 | 北京建筑大学 | Preparation device and preparation method of maifanite mineral water |
| CN104829018A (en) * | 2015-04-21 | 2015-08-12 | 俞权锋 | Chromium-containing waste water treatment method |
| CN107081142A (en) * | 2017-05-11 | 2017-08-22 | 重庆工商大学 | A kind of fluorine gas encloses the micro wave regeneration method of lower flyash with carbon dioxide mix atmosphere |
| CN107572628A (en) * | 2017-09-12 | 2018-01-12 | 奥为（天津）环保科技有限公司 | A kind of method for administering Acid Orange II simulated wastewater |
| CN109956690A (en) * | 2019-03-28 | 2019-07-02 | 天津中材工程研究中心有限公司 | A kind of domestic garbage incineration flyash processing method for cement industry |
| CN111068638A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for oxidation reaction and application thereof |
| US10882022B2 (en) | 2018-08-07 | 2021-01-05 | King Abdulaziz University | Method of removing organic pollutants from water using ball milled and sonicated oil fly ash powder |
| CN115043535A (en) * | 2022-06-14 | 2022-09-13 | 国信九天(湖北)环保科技集团有限公司 | High-chloride-ion wastewater treatment process |
| CN115812859A (en) * | 2022-12-23 | 2023-03-21 | 成都东方希望动物营养食品有限公司 | Vitamin premixed feed and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528911A (en) * | 2014-12-02 | 2015-04-22 | 北京建筑大学 | Preparation device and preparation method of maifanite mineral water |
| CN104829018A (en) * | 2015-04-21 | 2015-08-12 | 俞权锋 | Chromium-containing waste water treatment method |
| CN107081142A (en) * | 2017-05-11 | 2017-08-22 | 重庆工商大学 | A kind of fluorine gas encloses the micro wave regeneration method of lower flyash with carbon dioxide mix atmosphere |
| CN107572628A (en) * | 2017-09-12 | 2018-01-12 | 奥为（天津）环保科技有限公司 | A kind of method for administering Acid Orange II simulated wastewater |
| US10882022B2 (en) | 2018-08-07 | 2021-01-05 | King Abdulaziz University | Method of removing organic pollutants from water using ball milled and sonicated oil fly ash powder |
| US11110429B1 (en) | 2018-08-07 | 2021-09-07 | King Abdulaziz University | Method for removing polycyclic aromatic hydrocarbons from water using ball milled and sonicated oil fly ash powder |
| US11135563B1 (en) | 2018-08-07 | 2021-10-05 | King Abdulaziz University | Method for making a water treatment adsorbent filter |
| US11154837B2 (en) | 2018-08-07 | 2021-10-26 | King Abdulaziz University | Method for making absorbent oil fly ash powder |
| CN111068638A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for oxidation reaction and application thereof |
| CN109956690A (en) * | 2019-03-28 | 2019-07-02 | 天津中材工程研究中心有限公司 | A kind of domestic garbage incineration flyash processing method for cement industry |
| CN109956690B (en) * | 2019-03-28 | 2021-09-14 | 天津中材工程研究中心有限公司 | Method for treating fly ash generated by burning household garbage in cement industry |
| CN115043535A (en) * | 2022-06-14 | 2022-09-13 | 国信九天(湖北)环保科技集团有限公司 | High-chloride-ion wastewater treatment process |
| CN115812859A (en) * | 2022-12-23 | 2023-03-21 | 成都东方希望动物营养食品有限公司 | Vitamin premixed feed and preparation method thereof |
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Application publication date: 20140507 |