CN103359803B - A kind of water treatment method and device simultaneously removing heavy metal ions in wastewater and organic pollutant - Google Patents
A kind of water treatment method and device simultaneously removing heavy metal ions in wastewater and organic pollutant Download PDFInfo
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- CN103359803B CN103359803B CN201210103447.2A CN201210103447A CN103359803B CN 103359803 B CN103359803 B CN 103359803B CN 201210103447 A CN201210103447 A CN 201210103447A CN 103359803 B CN103359803 B CN 103359803B
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Abstract
The present invention relates to a kind of water treatment method and the device that can remove heavy metal ions in wastewater and organic pollutant simultaneously, belong to field of water pollution control.The present invention makes the heavy metal of continuous flow state-organic composite pollutant effluents flow through the high pressure pulse discharge district being filled with sorbent material, the organic pollutant of the various physical chemistry combined effect degraded adsorbent surface utilizing impulsive discharge to produce and around contiguous zone, obtain the active competitive adsorption point position of adsorbent surface, increase ABSORBENTS ABSORPTION metal biosorption, thus reach the object simultaneously removing heavy metal ion in waste water and organic pollutant.It is simple, easy to operate that the present invention has principle, heavy metal ion and all good advantage of organic pollutant removal effect.Be applicable to the process of heavy metal ion and organic compound contaminated waste water.
Description
Technical field
The invention belongs to technical field of water pollution control.In particular to a kind of water treatment method and the device of removing heavy metal ions in wastewater and organic pollutant simultaneously.The present invention is to the degradation mechanism of pollutent according to heavy metal ion and organic pollutant competitive adsorption principle on the sorbent and pulsed discharge plasma technology, the organic pollutant of the various physical chemistry combined effect degraded adsorbent surface produced by impulsive discharge and around contiguous zone, obtain the active competitive adsorption point position of adsorbent surface, increase ABSORBENTS ABSORPTION metal biosorption, thus reach the object simultaneously removing heavy metal ion in waste water and organic pollutant.
Background technology
The shortage of water resources and water environment pollution are the significant challenge that current mankind faces, and Ye Shi China realizes the top-priority significant problem of the strategy of sustainable development.Along with developing rapidly of the industry such as petrochemical complex, medicine, agricultural chemicals and dyestuff, quantity discharged containing various bio-refractory organic pollutant and heavy metal wastewater thereby is on the increase, organic pollutant in waste water and the quantity of heavy metal and kind grow with each passing day, and the various environmental problems caused thus have become significant problem affect human survival and health at present.
The process of single organic pollutant or heavy metal is only focused in Water Pollution Control Engineering research for a long time mostly, but organic pollutant and heavy metal are not well-separated in the water surrounding of reality, but is jointly present in same source of pollution or same environment.If dyeing waste water is exactly the combined pollution type trade effluent that typical hardly degraded organic substance and heavy metal ion coexist, not only containing a large amount of highly toxic dyestuffs, SYNTHETIC OPTICAL WHITNER, salt, acid, alkali in undressed dyeing waste water, also containing heavy metal elements such as cadmium, copper, zinc, chromium and iron; Also containing polytype pollutent in refinery water: heavy metals such as polycyclic aromatic hydrocarbons, ammonium salt, sulfide, prussiate, phenols, zinc, chromium; Other similar trade effluent is as the problem of costing wastwater, paper waste, intermetallic composite coating waste water, electroplating wastewater etc. also ubiquity organism and heavy-metal composite pollution.In addition, the industrial effluent treatment plant that the area collect at some municipal effluents and trade effluent merging, processed or industrial park focus on, can see both containing poisonous and harmful hardly degraded organic substance in waste water, equally again containing various heavy.In this kind of combined pollution waste water heavy metal and organic kind, content and existing forms different because of different manufacturing enterprise, wherein concentration of heavy metal ion is lower mostly, organic content is higher, complicated, processing requirements is very strict again, therefore, how economical, effectively remove organism in waste water and heavy metal and become an important topic in field of Environment Protection in recent years.
At present, for heavy metal-organic matter combined pollution waste water, domestic and international traditional treatment method is generally carried out in two steps: first heavy-metal ion removal, and main method has: (1) adds chemical agent makes it precipitate; (2) adopt air flotation technology, realize itself and aqueous phase separation; (3) by physical adsorption (as gac, graft starch, zeolite, diatomite etc.), heavy-metal ion removal; Utilize organic substance in the method degrading waste waters such as biology (as activated sludge process, biomembrance process etc.), chemical oxidation subsequently.The Measures compare of obvious conventional process heavy metal-organic matter combined pollution waste water is complicated, adds chemical reagent, both increases processing costs, cause secondary pollution again, and bring new pollutent into during pre-treatment in waste water; By Bubble-floating Method will pass into large quantity of air, therefore facility investment and process cost increase all greatly; Physisorphtion (as charcoal absorption) is although can effectively remove heavy metal in waste water and organic pollutant, but sorbent material easily reaches capacity, sorbent material need be regularly replaced, and have how to reclaim the problems such as heavy metal element, in addition absorption method fundamentally can not remove the organic pollutant in giving up, and is just transferred on sorbent material by organic pollutant.The traditional method of visible improvement heavy metal-organic matter combined pollution waste water can not meet current increasingly serious water pollutions situation, and there is many drawbacks.From technical feasibility and economical and efficient angle, research and develop the novel method of a kind of low stain, Low investment, process above-mentioned waste water and seem particularly important.
A kind ofly in organic wastewater with difficult degradation thereby process, apply more corona discharge plasma form by high-voltage pulse power source as the pulse-streamer corona discharge plasma body that additional power source is formed.As the one in advanced oxidation water technology, pulsed discharge plasma technology has plurality of advantages compared with other high-level oxidation technology, comprise: the direct impulsive discharge in the aqueous solution can operate at normal temperatures and pressures, just can produce the Chemical oxidizing species oxidative degradation organism of original position in whole discharge process in aqueous without the need to adding catalyzer, this technology to the process economy of low-concentration organic and effectively; In addition, the reactor types of apply pulse discharge plasma water technology can adjust flexibly, and the process of operation is simple, and corresponding maintenance cost is also lower.But the problem that for a long time, in pulsed discharge plasma system, contaminant degradation energy efficiency is low is the key issue affecting its application always.For this reason, many scholars propose pulsed discharge plasma technology and other oxidative species, advanced oxidation processes or physical action to join together degradation of contaminant, thus improve this Technology Energy efficiency.Be not difficult to find, although pulsed discharge plasma technology and other combine with technique can improve the energy efficiency of contaminant degradation effectively, they are just for the organic pollutant in waste water, and helpless for heavy metal-organic matter combined pollution waste water.Given this, and the deficiency that current sorbent material exists in heavy metal and organic polluting water process, the present invention proposes pulsed discharge plasma technology to combine for removing while heavy metal ions in wastewater and organic pollutant with adsorbent technology.
Summary of the invention
Object of the present invention is just to provide that a kind of processing efficiency is high, convenient operation and management and do not produce secondary pollution, and can remove water treatment method and the device of metal ion and organic pollutant in waste water simultaneously.
Basic ideas of the present invention are: sorbent material is a concentration center, its surface and around contiguous zone by adsorbing the environment first createing high density, then the organic pollutant of various physics and chemistry effects degraded adsorbent surface and the surrounding contiguous zone thereof formed in process of pulse discharge is utilized, reduce energy consumption on the one hand, improve the degradation efficiency of organic pollutant; The on the other hand active competitive adsorption point position of release sorbent material, increases ABSORBENTS ABSORPTION metal biosorption ability, extends the work-ing life of sorbent material, finally reaches being separated and removal of heavy metal ion in waste water and organic pollutant.
Technical solution of the present invention is:
I () sorbent material (7) is common commercially available gac, silica gel, aluminum oxide, molecular sieve or natural clay.When the sorbent material (7) used is granular gac, silica gel, aluminum oxide, molecular sieve or natural clay, the particle size range of sorbent material (7) is 0.5mm-20mm; When the sorbent material (7) used is pulverous gac, silica gel, aluminum oxide, molecular sieve or natural clay, the particle size range of sorbent material (7) is 2 order-250 orders.
(ii) technique simultaneously removed of heavy metal ions in wastewater and organic pollutant:
The first step, open air valve (13), air-blowing in reactor (2), then the pending waste water containing heavy metal ion and organic pollutant and sorbent material (7) is allowed to be in region of discharge in reactor (2), sorbent material (7) volume is 0-0.8 with the scope of the ratio of pending wastewater volume, closed reactor (2);
Second step, closed electrical source switch (18), the frequency of regulating impulse power supply (1) and output voltage, between pin hole electrode (3) and plate electrode (5), form stable corona discharge, streamer-discahrge or glow discharge, discharge time is 0.5min-12h;
3rd step, after electric discharge terminates, makes zero the output voltage of the pulse power (1), cut-off switch (18), open reactor (2), the waste water processed and sorbent material (7) are taken out from reactor (2), process terminates.
Device of the present invention is formed primarily of the pulse power (1), reactor (2) and utility appliance.
The pulse power (1) refers to two positive and negative pulse power, direct impulse voltage and negative-going pulse voltage all can independently regulate, the frequency-tuning range of the pulse power (1) is 0Hz-200Hz, peak impulse voltage regulation range is 0kV-500kV, and pulse power regulation range is 0kW-200kW.Reactor (2) is made up of pin hole electrode (3), metal sheet (4), plate electrode (5), metal screw (6), inlet mouth (8) and offgas outlet (9); When needing to allow the pending waste water in reactor (2) be in recurrent state, reactor (2) also comprises water-in (10) and water outlet (11).Pin hole electrode (3) is aperture is 1mm-100mm, and the long metal needle for 5mm-500mm, being fixed on thickness is 1mm-1000mm, and area is 100mm
2-10m
2circular metal plate (4) on, upper uniform distribution 1-3 root pin hole electrode (3) of every square centimeter of metal sheet (4); Plate electrode (5) is thickness is 1mm-1000mm, and area is 50mm
2-8m
2circular metal plate, reactor (2) top is fixed on by metal screw (6), plate electrode (5) namely can be immersed in pending waste water, also can be placed in the ullage of pending waste water, and preventing board electrode (5) corrodes; Distance between plate electrode (5) and pin hole electrode (3) syringe needle can be passed through metal screw (6) and regulate, and regulation range is 1mm-5m; High-voltage output end series connection protective resistance (17) of the pulse power (1) is connected on metal sheet (4), low-voltage output tandem tap (18) and metal screw (6) the together ground connection of the pulse power (1).
Utility appliance is determined according to technique during application.Comprising the control device such as protective resistance (17), switch (18) giving power supply supporting.In order to allow, reactor (2) is middle produces a large amount of active species, need to injecting gas in reactor (2), therefore also need in device to be equipped with gas cylinder (12), air valve (13) and exhaust gas absorption cell (14); Gas is injected by gas cylinder (12), through air valve (13), then enter in reactor (2) by inlet mouth (8), finally discharge from offgas outlet (9) and enter exhaust gas absorption cell (14); Because tail gas contains a large amount of active specy such as ozone, tail gas can be re-injected in reactor (2), the object improving treatment effect can be reached like this, meanwhile, not need again the device processing tail gas, decrease the generation of secondary pollution; The gas blasted in reactor (2) is the gases such as air, oxygen, nitrogen, ozone and argon gas, and wherein, air is 0%-100%, and oxygen is 0%-100%, and nitrogen is 0%-100%, and ozone is 0%-100%, and argon gas is 0%-100%.In order to improve processing load and the efficiency of reactor (2), the pending waste water in reactor (2) can be allowed to be in recurrent state, therefore also needing in device to be equipped with liquid storage bottle (15) and peristaltic pump (16); Pending waste water in liquid storage bottle (15) enters in reactor (2) by peristaltic pump (16) through water-in (10), then got back in liquid storage bottle (15) by water outlet (11), realize the circulation of waste water.
For a kind of water treatment method removing heavy metal ions in wastewater and organic pollutant described in the present invention simultaneously, the sorbent material adopted (7) is not only gac, silica gel, aluminum oxide, molecular sieve and natural clay, can also be loaded with TiO
2, metal (Ag, Au, Pb, Mn etc.) catalyzer sorbent material.
Reactor (2) shelling machine can be made into square or cuboid-type for a kind of water treatment device removing heavy metal ions in wastewater and organic pollutant described in the present invention simultaneously, now, metal sheet (4) and plate electrode (5) are square or cuboid-type.
About a kind of determination of removing heavy metal ions in wastewater and the water treatment method of organic pollutant and the operating parameter of device simultaneously, must be noted that the problem of the following aspects:
When a. injecting waste water in reactor (2), first will to air-blowing in reactor (2), otherwise waste water can flow to the bottom of reactor (2) by pin hole electrode (3), leave electrical discharge zone, do not reach the object of process waste water.
B. guarantee that the syringe needle of every root pin hole electrode (3) is consistent with the distance of plate electrode (5), if inconsistent, shelf depreciation can occur, affect the treatment effect of waste water.
C. the output voltage of slow regulating impulse power supply (1), between pin hole electrode (3) and plate electrode (5), forms stable corona discharge, streamer-discahrge or glow discharge.
When d. needing to pass into gas in reactor (2), gas flow rate in reactor (2) can not be too large, otherwise, large bubble can be formed in reactor (2), cause unstable electric discharge, the high reactivity species produced that simultaneously discharge do not act on pollutent and are just taken out of reactor (2), are unfavorable for the removal of pollutent, and waste energy.
E. need to allow waste water circulation pending in reactor (2) time, the flow velocity of waste water circulation can not be too large, otherwise, unstable shelf depreciation can be produced, affect the removal effect of pollutent.
The pore of blocking pin hole electrode (3) when f. avoiding filling sorbent material (7) in reactor (2), prevents uneven electric discharge.
When adopting water treatment method and the device of a kind of removal heavy metal ions in wastewater and organic pollutant simultaneously of the present invention, precaution:
(1) exactness and the security of power supply system is checked.
(2) resistance to air loss of reactor (2) to be guaranteed, prevent the leakage of the tail gas such as ozone.
The beneficial effect that the present invention reaches and benefit are combined with chemical adsorbing separation engineering by a kind of new electrotechnology one pulsed discharge plasma technology that fast development is got up in recent years, be applied in heavy metal-organic matter combined pollution wastewater treatment.The method has that processing efficiency is high, convenient operation and management and do not produce the advantages such as secondary pollution.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
Fig. 1 of the present inventionly a kind ofly removes heavy metal ions in wastewater and the water treatment method of organic pollutant and the system schematic of device simultaneously.
Fig. 2 is the schematic perspective view of cylinder type reactor (2) of the present invention.
Fig. 3 is plate electrode (5) schematic front view in liquid level in cylinder type reactor (2) of the present invention.
Fig. 4 is the schematic top plan view of cylinder type reactor (2) of the present invention.
Fig. 5 is the schematic top plan view of square build reactor (2) of the present invention.
Fig. 6 is the schematic front view of the middle plate electrode (5) of cylinder type reactor (2) of the present invention at ullage.
In figure: 1. the pulse power, 2. reactor, 3. pin hole electrode; 4. metal sheet, 5. plate electrode, 6. metal screw; 7. sorbent material, 8. inlet mouth, 9. offgas outlet; 10. water-in, 11. water outlets, 12. gas cylinders; 13. air valves, 14. exhaust gas absorption cells, 15. liquid storage bottles; 16. peristaltic pumps, 17. protective resistances, 18. switches.
Embodiment
As shown in Figure 1, the pulse power (1) adopts direct impulse to the device adopted in this example, and frequency is 24Hz, and peak impulse voltage regulation range is 0kV-50kV.Reactor (2) shell is made up of synthetic glass, and shape is diameter is 100mm, and height is the right cylinder of 150mm.In this example, plate electrode (5) is diameter is 80mm, and thickness is the stainless steel plectane of 5mm, is immersed in pending waste water; Pin hole electrode (3) is 76
#medical needle, being evenly distributed in diameter is 90mm, and thickness is on the circular metal plate (4) of 3mm, and the distance between two pin hole electrodes (3) is 15mm; Distance between the syringe needle of every root pin hole electrode (3) and plate electrode (5) is 15mm; The gas passed in reactor (2) is air; Sorbent used (7) are column coal mass active carbon, and diameter is 1.5mm, and mean length is 3mm, and gac amount of fill is 2.0g; In addition the utility appliance such as gas cylinder (12), air valve (13), exhaust gas absorption cell (14), liquid storage bottle (15), peristaltic pump (16), protective resistance (17) and power switch (18) with under meter is used in this example.
In this example, choose commercially available chemical pure Cadmium chloride fine powder and phenol as handling object, be made into Cd
2+simulation heavy metal-organic composite pollutant effluents that concentration is 20mg/L, phenol concentration is 100mg/L, adopt a kind of water treatment method and the device simultaneously removing heavy metal ions in wastewater and organic pollutant in the present invention, carry out heavy metal ions in wastewater and organic pollutant removal test, step is:
The first step, checks exactness and the security of power supply system, and guarantees the resistance to air loss of reactor (2).
Second step, discharge process, treatment process is:
First, be positioned over by 2.0g gac in reactor (2), closed reactor (2), open air valve (13), in reactor (2), blast air, gas flow is 6L/min; Open peristaltic pump (16), contain Cd by liquid storage bottle (15)
2+be injected in reactor (2) with the pending waste water of phenol, wastewater volume is 250mL.
Secondly, closed electrical source switch (18), the frequency of regulating impulse power supply (1) is 24Hz, and peak impulse voltage is 25.4kV, form stable corona discharge in waste water between pin hole electrode (3) and plate electrode (5), discharge time is 15min.
Finally, treatment effect analysis, samples from liquid storage bottle (15) every 3min, analyzes the Cd in waste water
2+and phenol concentration; Detect the increase found along with discharge time, Cd in waste water
2+reduce gradually with phenol concentration.After the process of 15min, Cd
2+processing efficiency be 18.4%, the processing efficiency of phenol is 49.1%.
3rd step, after electric discharge terminates, the output voltage of the pulse power (1) is made zero, cut-off switch (18), then the waste water processed is discharged by peristaltic pump (16) from reactor (2), turn off peristaltic pump (16) and air valve (13), open reactor (2), take out sorbent material (7), process terminates.
In order to determine phenol and Cd
2+removal effect mainly by impulsive discharge Pyrogentisinic Acid Degradation and cause sorbent material (7) surface to Cd
2+the increase of adsorption site position causes, and has carried out again test below:
The first, be positioned over by 2.0g gac in reactor (2), closed reactor (2), then open air valve (13), drum air in reactor (2), gas flow is 6L/min; Open peristaltic pump (16), contain Cd by liquid storage bottle (15)
2+be injected in reactor (2) with the pending waste water of phenol, wastewater volume is 250mL.
The second, analyze Cd in liquid storage bottle (15)
2+and phenol concentration, analytical results finds after the absorption of 15min, Cd
2+clearance be 5.6%, the processing efficiency of phenol is 19.3%.This illustrates, the removal of phenol in wastewater is mainly caused by impulsive discharge, Cd
2+removal be also mainly phenol on impulsive discharge degrading activity charcoal, make activated carbon surface obtain more adsorption site position, thus add gac to Cd
2+adsorptive capacity, improve Cd
2+clearance.
Claims (8)
1. remove a water treatment device for heavy metal ions in wastewater and organic pollutant simultaneously, it is characterized in that, be made up of the pulse power (1) and reactor (2), the pulse power (1) is two positive and negative pulse powers, direct impulse voltage and negative-going pulse voltage all can independently regulate, the frequency-tuning range of the pulse power (1) is 0Hz-200Hz, and peak impulse voltage regulation range is 0kV-500kV, pulse power regulation range is 0kW-200kW, reactor (2) is made up of pin hole electrode (3), metal sheet (4), plate electrode (5), metal screw (6), and sorbent material is placed in the region of discharge of reactor, pin hole electrode (3) is aperture is 1mm-100mm, and the long metal needle for 5mm-500mm, being fixed on thickness is 1mm-1000mm, and area is 100mm
2-10m
2circular metal plate (4) on, plate electrode (5) is thickness is 1mm-1000mm, and area is 50mm
2-8m
2circular metal plate, is fixed on reactor (2) top by metal screw (6), plate electrode (5) is 1mm-5m with the regulation range of the spacing of pin hole electrode (3) syringe needle, high-voltage output end series connection protective resistance (17) of the pulse power (1) is connected on metal sheet (4), low-voltage output tandem tap (18) and metal screw (5) the together ground connection of the pulse power (1), reactor (2) up and down two ends correspondence is provided with offgas outlet (9) and gas inlet (8), gas inlet (8) is connected with gas cylinder (12) through air valve (13), offgas outlet (9) is connected with exhaust gas absorption cell (14), reactor (2) up and down both sides correspondence is provided with water outlet (11) and water-in (10), water-in (10) is connected with liquid storage bottle (15) through peristaltic pump (16), water outlet (11) is connected with liquid storage bottle (15).
2. a kind of water treatment device simultaneously removing heavy metal ions in wastewater and organic pollutant according to claim 1, it is characterized in that, plate electrode (5) is immersed in pending waste water.
3. a kind of water treatment device simultaneously removing heavy metal ions in wastewater and organic pollutant according to claim 1, it is characterized in that, plate electrode (5) is positioned at pending waste water ullage.
4. use a kind of water treatment device simultaneously removing heavy metal ions in wastewater and organic pollutant described in claim 3 to carry out the method for wastewater treatment, it is characterized in that, the pulse power (1) exports high pressure, be applied in the heavy metal-organic composite pollutant effluents being filled with sorbent material (7) between metal sheet (4) and plate electrode (5), the spacing of adjustment plate electrode (5) and pin hole electrode (3) syringe needle, the pulse power (1) frequency and the pulse power (1) output voltage peak value, make to form stable corona discharge between plate electrode (5) and pin hole electrode (3) syringe needle, streamer-discahrge or glow discharge, the organic pollutant of the various physics and chemistry effect degraded adsorbent surface that impulsive discharge produces and around contiguous zone, obtain the active competitive adsorption point position of adsorbent surface, increase ABSORBENTS ABSORPTION metal biosorption, reach the object simultaneously removing heavy metal ion in waste water and organic pollutant.
5. method according to claim 4, it is characterized in that, sorbent material (7) is filled in the heavy metal-organic composite pollutant effluents between metal sheet (4) and plate electrode (5), and the sorbent material (7) of filling is common commercially available granular gac, silica gel, aluminum oxide, molecular sieve or natural clay; The particle size range of sorbent material is 0.5mm-20mm; Sorbent material (7) volume added is 0.8 with the ratio of pending wastewater volume.
6. method according to claim 4, it is characterized in that, sorbent material (7) is filled in the heavy metal-organic composite pollutant effluents between metal sheet (4) and plate electrode (5), the sorbent material (7) of filling is common commercially available pulverous gac, silica gel, aluminum oxide, molecular sieve or natural clay, and the particle size range of sorbent material is 2 order-250 orders; Sorbent material (7) volume added is 0.8 with the ratio of pending wastewater volume.
7. method according to claim 4, is characterized in that, processing step is:
The first step, open air valve (13), air-blowing in reactor (2), is then placed in the region of discharge of reactor (2), closed reactor (2) by the pending waste water containing heavy metal ion and organic pollutant and sorbent material (7);
Second step, closed electrical source switch (18), the frequency of regulating impulse power supply (1) and output voltage, between pin hole electrode (3) and plate electrode (5), form stable corona discharge, streamer-discahrge or glow discharge, discharge time is 0.5min-12h;
3rd step, after electric discharge terminates, the output voltage of the pulse power (1) is made zero, cut-off switch (18), open reactor (2), the waste water processed and sorbent material (7) are taken out from reactor (2).
8. method according to claim 7, it is characterized in that, in a first step, the gas blasted in reactor (2) is air, oxygen, nitrogen, ozone and argon gas, and wherein, air is 0%-100%, oxygen is 0%-100%, nitrogen is 0%-100%, and ozone is 0%-100%, and argon gas is 0%-100%.
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CN113526753A (en) * | 2021-07-30 | 2021-10-22 | 南京工业大学 | Method for treating phenolic wastewater by coupling high-voltage pulse discharge with molybdenum disulfide |
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