CN106006946A - Electrolytically modified quartz sand filter bed and application thereof - Google Patents

Electrolytically modified quartz sand filter bed and application thereof Download PDF

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Publication number
CN106006946A
CN106006946A CN201610356443.3A CN201610356443A CN106006946A CN 106006946 A CN106006946 A CN 106006946A CN 201610356443 A CN201610356443 A CN 201610356443A CN 106006946 A CN106006946 A CN 106006946A
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China
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quartz sand
filter bed
sand filter
electrolysis
phosphorus
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Inventor
杨柳燕
高燕
郭琼
王楚楚
魏儒平
张瑄文
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Nanjing University
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Nanjing University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/104Granular carriers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The invention discloses an electrolytically modified quartz sand filter bed in which a bio-ceramsite layer and a quartz sand layer are sequentially arranged from the bottom up, wherein an aeration device is arranged in the bio-ceramsite layer; a cathode plate and an anode plate are arranged in the quartz sand layer, and are respectively connected with the cathode and the anode of a DC stabilized power supply. Compared with the prior art, the electrolytically modified quartz sand filter bed has the advantages that as the quartz sand filter bed technology and the electrolysis technology are used in a combined manner, loading of metal hydroxide on the surface of quartz sand is realized under the action of short-term electrolysis, the modification of the quartz sand filter bed is realized, no secondary pollution is generated, the environment friendliness is high, and the adsorption efficiency of a trace amount of phosphorus in water is improved. According to the electrolytically modified quartz sand filter bed technology, the phosphorus removing function of the quartz sand filter bed is strengthened, the trace amount of phosphorus can be removed effectively in a relatively short hydraulic retention time, the phosphorus concentration of outlet water is remarkably lower than that of the quartz sand filter bed, the effect is continuous and efficient, the electrolytically modified quartz sand filter bed is not easy to block, and a new technology is provided for effectively improving the biological stability of urban water supply plants.

Description

A kind of electrolysis Modified Quartz Sand filter bed and application thereof
Technical field
The invention belongs to water treatment field, be specifically related to a kind of electrolysis Modified Quartz Sand filter bed and application thereof.
Background technology
China's major part water source is polluted by organic matter seriously, even if passing through the drinking water that sterilization is qualified in urban water plant, During urban district carries, the heterotrophic bacterial in water still has the phenomenon increased, and this is considered as instability biology of water Property causes.Biology, the potable water network tube wall of instability can form certain thickness biomembrane, corrodes pipeline, reduction Pipe network conveyance power of water, causes the secondary pollution of water quality, and constitutes a threat to the health of the mankind.Developing country has every year Child's morbidity or dead of less than 12200000 five years old, dies from diarrhoea more than 3,000,000 people, is wherein mostly due to drink and is subject to Caused by the water that microorganism is polluted.
For the phenomenon of the pipe network instability that difference bacterium is caused, the most conventional measure controlling pipe network difference bacterium mainly has: (1) rinse pipe network, increase the injected volume of disinfectant or use other disinfectant instead;(2) corrosion inhibitor is used;(3) Controlling the nutrient inventory in water body, the factor controlling nutrient mainly has: organic carbon controlling elements, phosphorus controlling elements. Phosphorus is one of element required in microbial metabolism, it is considered that the carbon-phosphorus ratio needed for growth of microorganism is 100:1, In drinking water, required carbon-phosphorus ratio is lower slightly for 100:(1.7~2.0).For this situation, using phosphorus as controlling elements, reduce Phosphorus content in tap water, can effectively control the content of microorganisms in water body, from not up to Biostatic.
The method that conventional phosphorus processes has chemical precipitation method (such as iron salt, aluminium salt and calcium salt etc.), bioanalysis and absorption method. The chemical precipitation of phosphorus is divided into 4 steps: precipitation, cohesion, flocculation and solid-liquid separation.Chemical precipitation method Dephosphorization efficiency higher, water outlet TP content can meet the requirement of 1mg/L.In Water purification, the removal of phosphorus is mainly by mixed Retrogradation is formed sediment and filters two stages, and what coagulation effect was good can remove major part phosphorus, and another small part phosphorus relies on filtering technique and goes Remove.Absorption method has that sludge output is few, reusable and the advantage such as economical and efficient, and to the micropollution removed in water Thing has the advantage of uniqueness.Therefore, the method removing trace amounts of phosphorus is filtered in research, selects high-quality filtrate, optimizes filtercondition, It is an important channel for ensureing the biological stability of water outlet.
The adsorbent of research mainly has at present: red mud, flyash, apatite, zeolite, biomass carbon etc..Quartz sand is made Also being widely used in sewage disposal for a kind of material simple and easy to get, at present, conventional quartz sand material is the most right It is applied after being modified again, and general method of modifying is to enter at surface metal oxide and the hydroxide of quartz sand Row surface modification, it is possible to change the quantity of its surface potential and adsorption functional group, improves the filtrate removal to water pollutant Efficiency.The method of quartz sand modification mainly has iron salt, magnesium salt, aluminium salt etc., different according to its process pollutant purpose.With In remove trace amounts of phosphorus quartz sand method of modifying mainly based on iron salt and aluminium salt, wherein iron salt is to quartz sand study on the modification relatively Many, it is coated with ferrum Modified Quartz Sand, as a kind of filtrate, there is stronger absorption property, be widely used to remove respectively during water processes Plant pollutant.Wang Junling etc. (2007) have studied the painting ferrum Modified Quartz Sand Filtration Adsorption performance to trace amounts of phosphorus, research knot Fruit proves that the quartz sand of ferrum modification has good removal effect to trace amounts of phosphorus hydrochlorate, and the clearance of phosphorus is changed by Modified Quartz Sand More than 90%, wherein use is material modified for iron chloride.Xu Guangmei etc. (2007) are with Fe (NO3)·9H2O is modifying agent, It is prepared as modified sand filtering material at 110 DEG C, and the adsorption isotherm and thermokinetics to its adsorption and dephosphorization is studied.Lu Build and utilize ferrum Modified Quartz Sand filtering technique to carry out the regeneration technology of Treating Municipal Sewage in (2008) years such as ripple, find it Preferable to the clearance of phosphorus, after its filtration, the aqueous concentration of phosphorus is below 1mg/L.Described in document above, quartz sand is changed Property method, usually utilizes iron chloride, aluminum chloride etc. to soak, and modified can produce certain pollution waste liquid.Therefore, It is applied on a large scale and need nonetheless remain for further being improved.
For the problems referred to above, electrochemical techniques are applied among the modification of quartz sand by the present invention, through electrolysis produced Quartz sand surface is carried out loaded modified by metal hydroxides, utilizes the Modified Quartz Sand filtering technique strengthening suction to trace amounts of phosphorus Attached removal, forms efficient electrolysis Modified Quartz Sand depth filtration, deep bed filtration technology, Modified Quartz Sand have bigger specific surface area and Ion-exchange capacity, has bigger exchange capacity of absorption to the phosphorus in water body, and its surface can form stable biology simultaneously Film.The absorption making microorganism goes dephosphorization to combine utilization with quartz sand absorption exchange interaction, and reach stability and high efficiency removes eliminating minute The ability of phosphorus.This electrolysis Modified Quartz Sand filter bed technology can effectively remove the trace amounts of phosphorus in water body, and process is simple Environmental friendliness, is conducive to the upgrading in filter tank in existing water treatment technology, thus has good using value.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of electrolysis Modified Quartz Sand filter bed, with solve prior art exist right The problem that in water body, the removal effect of trace amounts of phosphorus is the best.
The present invention also to solve the technical problem that the application being to provide above-mentioned electrolysis Modified Quartz Sand filter bed.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
A kind of electrolysis Modified Quartz Sand filter bed, in filter bed, paving is sequentially provided with biological ceramic particle layer and quartz sand layer from bottom to up;
Wherein, it is provided with aerator in biological ceramic particle layer;Being provided with minus plate and positive plate in quartz sand layer, positive plate is with cloudy Pole plate intersects to be placed, and minus plate is connected with negative pole and the positive pole of D.C. regulated power supply respectively with positive plate.
Wherein, preferably positive plate immediate with biological ceramic particle layer.
Wherein, the thickness of biological ceramic particle layer and quartz sand layer is than for 1:9~14.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that in described biological ceramic particle layer, biological ceramic particle Particle diameter is 3~5mm;In described quartz sand layer, the particle diameter of quartz sand is 1~1.5mm.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that the plate spacing between adjacent minus plate and positive plate With the gross thickness of quartz sand filter than for 1:3~5.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that be equipped with diameter on minus plate and positive plate The limbers of 0.5~1cm, the distance between adjacent two limbers is 1~2cm.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that the material of described positive plate is ferrum or magnalium conjunction Gold, the material of described minus plate is ferrum.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that minus plate and positive plate in filter bed total effectively Volume is 0.00008~0.005:1 with the volume ratio of quartz sand filtering layer in filter bed.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that the aeration rate of described aerator is 2~18L/min.
Wherein, the effect of the aeration aerating bottom filter bed mainly has:
(1) it is beneficial to ferrous oxidising one-tenth ferric iron in electrolysis, thus promotes the generation of hydrated ferric oxide. in water body;
(2) the distribution ratio making hydrated ferric oxide. in water body after aeration is more uniform, is beneficial to hydrated ferric oxide. at quartz sand table The appendix in face;
(3) environment that maintenance is the most aerobic, it is to avoid the reduction of three rank ferrum, thus inhibit the secondary of phosphorus to discharge.
Wherein said electrolysis Modified Quartz Sand filter bed, it is characterised in that the voltage of described D.C. regulated power supply is 2~20V.
Above-mentioned electrolysis Modified Quartz Sand filter bed in the application removed in water body in phosphorus and heavy metal also at the protection model of the present invention Within enclosing.
When utilizing above-mentioned electrolysis Modified Quartz Sand filter bed to remove the phosphorus in water body or heavy metal, by treatment sewage from the bottom of filter bed Portion is injected in filter bed;When filter bed runs, the ferrous ion that positive plate is electrolysed out is easier to generate trivalent in the case of aeration Ferrum, ferric iron and the OH in water body-Generating hydroxide, this hydrated ferric oxide. can be supported on quartz sand surface, be electrolysed simultaneously The ferrous ion gone out and three rank iron ions also can form precipitation with phosphate, and hydrated ferric oxide. also can be to the phosphorus in water body simultaneously Hydrochlorate carries out flocculation sediment.Quartz sand after load iron, can significantly improve the specific surface area of quartz sand, is beneficial to poly- The attachment of phosphorus microorganism also forms stable biomembrane.In a word, the quartz sand after ferrum is loaded modified and quartz sand surface Biomembrane and water body in hydrated ferric oxide. etc., by settling, filter, adsorbing, the physics such as the Absorption And Metabolism of microorganism Chemical thermogenesis so that quartz sand filter can efficiently remove trace amounts of phosphorus in shorter hydraulic detention time.
Beneficial effect: compared with prior art, the present invention has the advantage that
1, by quartz sand filter technology is used in conjunction with electrolysis tech, under the electrolysis of short time, it is achieved that quartz The load of sand surface metal hydroxide, it is achieved that the modifying function of quartz sand filter, does not produce secondary pollution simultaneously, Environmental friendliness, improves the effect of trace amounts of phosphorus in its adsorbed water body.
2, electrolysis Modified Quartz Sand filter bed technology, enhances quartz sand filter and goes the effect of dephosphorization, it is achieved that trace The phosphorus effective removal in shorter hydraulic detention time, and in water outlet, the concentration of phosphorus is substantially less than quartz sand filter, continues Efficiently, and it is not easily blocked, provides new technology for the effective biological stability solving urban water plant.
Accompanying drawing explanation
Fig. 1 is electrolysis Modified Quartz Sand filter bed system structure schematic diagram in embodiment 1;
Fig. 2 is the electrolysis Modified Quartz Sand filter bed clearance to trace amounts of phosphorus in embodiment 1.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on not described in detail in claims The present invention.
Sewage used in following embodiment configures with reference to urban water plant low phosphorus.Simulation sewage is by analytically pure Potassium dihydrogen phosphate prepare, pollutant mainly based on the phosphorus of low concentration, its PO4 3--P concentration is 50 μ g/L, the stream of sewage Dynamic direction is from bottom to top, and sewage hydraulic detention time in electrolysis filter bed device is 2h.
In following embodiment, the pH of Inlet and outlet water, dissolved oxygen (DO), oxidation-reduction potential (ORP), temperature (DEG C) are respectively Use the portable dissolved oxygen instrument of HachHQ30-d (LDO101 standard type dissolved oxygen electrode), the portable pH meter of Hach (PHC101 standard type pH electrode), soil redox potential meter (DMP-2 digital display MV/pH/ thermometer) and water temperature Meter (JZLCWQG-17) is measured.The mensuration of low concentration phosphoric acid uses peacock green phosphato-molybdic heteropolyacid spectrophotography (ginseng See the standard in " water and effluent monitoring analyze method (fourth edition) ") at 620nm, measure concentration;Iron ion uses neighbour Phenanthroline spectrophotography (seeing the standard in " water and effluent monitoring analyze method (fourth edition) ") is surveyed at 510nm Determine concentration.Each sample uses ultraviolet spectrophotometry (V1800, SHIMADZU) point through standardization program after processing Analysis measures.
Embodiment 1
As it is shown in figure 1, the analog being electrolysed Modified Quartz Sand filter bed that laboratory builds, it is by filter bed 1, electrolysis system 2-3 and aerating system 3 form;There is biological ceramic particle layer 1-2 the bottom of filter bed as bed course, and particle diameter is 3~5mm, and volume accounts for filter The 7% of bed cumulative volume;Filter bed top is quartz sand layer 1-1, and particle diameter is 1~1.5mm, and volume accounts for the 93% of filter bed cumulative volume. The bottom of filter bed is provided with water inlet, and the sidewall of device upper end arranges outlet.Identical electroless system is set simultaneously Device is matched group.
Be provided with one piece of positive plate and one piece of minus plate in the inside of the quartz sand filter media of filter bed, its material is ferrum, and anode Plate is positioned at the top of filter bed, and minus plate is positioned at the bottom of filter bed, and plate spacing is 10cm.Negative electrode and positive plate surface every 1cm is covered with the limbers of 0.5cm.Anode is by producing iron ion under the effect of electrolysis, it is provided that for quartz sand filter The modified hydrated ferric oxide. used.Positive plate effective volume in quartz sand filter with the volume ratio processing filtrate is 0.0036.Minus plate is connected with D.C. regulated power supply with positive plate, and during cell reaction, voltage is 5V, and electric current is 0.001A.The sewage being beneficial to conduction is first full of filter bed as electrolyte before starting by cell reaction, then connects power supply and carries out Cell reaction, the cell reaction time is 48h.Carry out during cell reaction bottom aeration, its aeration rate be 2~ 3L/min, is uniformly attached to the surface of quartz sand by the iron ion produced in aeration beneficially electrolytic process.Carry out dirt afterwards The dephosphorization treatment of water, in its processing procedure, the time of staying of low-concentration phosphorus-containing sewage is 2h, and the cell reaction time is 1h/d, Aerator works 2h continuously.
After pending low-concentration phosphorus-containing sewage flows into electrolysis modification biological filter bed, the ferrous ion that positive plate is electrolysed out exists It is easier to generate ferric iron, ferric iron and the OH in water body in the case of aeration-Generating hydroxide, this hydrated ferric oxide. can be born Being loaded in quartz sand surface, the ferrous ion being simultaneously electrolysed out and three rank iron ions also can form precipitation, simultaneously with phosphate Hydrated ferric oxide. also can carry out flocculation sediment effect to the phosphate in water body.Having aeration head bottom filter bed, its effect is main Have: (1) is beneficial to ferrous oxidising one-tenth ferric iron in electrolysis, thus promotes the generation of hydrated ferric oxide.;(2) make in water body The distribution ratio of hydrated ferric oxide. is more uniform, is beneficial to ferrum at the appendix of quartz sand surface;(3) environment that maintenance is the most aerobic, Avoid the reduction of three rank ferrum, thus inhibit the secondary of phosphorus to discharge.Quartz sand after load iron, can significantly improve The specific surface area of quartz sand, the attachment of the most poly-phosphorus microorganism also forms stable biomembrane.In a word, change through ferrum load Hydrated ferric oxide. etc. in the biomembrane of the quartz sand after property and quartz sand surface and water body, by settling, filter, adsorbing, The physical chemistry biological agents such as the Absorption And Metabolism of microorganism so that quartz sand filter can be in shorter hydraulic detention time Efficiently remove trace amounts of phosphorus, efficiently solve Biostatic sex chromosome mosaicism.
Result of the test is as shown in Figure 2.In process group, the phosphatic removal effect of low concentration is apparently higher than matched group.PO4 3--P Content in process group is only 0.76ug/L, and clearance is 98.4%, and the content in matched group is by the initial stage 20.9ug/L, clearance is 58.2%, differs 40.2% between the two.Its clearance in quartz sand filter is the lowest In the modified filter bed group of electrolysis, it is therefore evident that, the quartz sand filter after being loaded by electrolysis Modified Iron is in water outlet The removal effect of phosphorus is substantially better than matched group.

Claims (10)

1. an electrolysis Modified Quartz Sand filter bed, it is characterised in that in filter bed, paving is sequentially provided with biological ceramic particle from bottom to up Layer and quartz sand layer;Wherein, it is provided with aerator in biological ceramic particle layer;The minus plate that intersection is placed it is provided with in quartz sand layer With positive plate, minus plate and positive plate are connected with negative pole and the positive pole of D.C. regulated power supply respectively.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that biological ceramic particle layer and quartz The thickness of layer of sand is than for 1:9~14.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that described biological ceramic particle layer In, the particle diameter of biological ceramic particle is 3~5mm;In described quartz sand layer, the particle diameter of quartz sand is 1~1.5mm.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that adjacent minus plate and sun The gross thickness of the plate spacing between pole plate and quartz sand filter is than for 1:3~5.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that on minus plate and positive plate Being equipped with the limbers of diameter 0.5~1cm, the distance between adjacent two limbers is 1~2cm.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that the material of described positive plate Material is ferrum or magnalium, and the material of described minus plate is ferrum.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that minus plate and positive plate are in filter Total effective volume in Chuan is 0.00008~0.005:1 with the volume ratio of quartz sand filtering layer in filter bed.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that the exposure of described aerator Tolerance is 2~18L/min.
Electrolysis Modified Quartz Sand filter bed the most according to claim 1, it is characterised in that described D.C. regulated power supply Voltage be 2~20V.
10. the electrolysis Modified Quartz Sand filter bed described in claim 1 is in the application removed in water body in phosphorus and heavy metal.
CN201610356443.3A 2016-05-26 2016-05-26 Electrolytically modified quartz sand filter bed and application thereof Pending CN106006946A (en)

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