CN208136016U - A kind of arsenic-containing waste water processing unit - Google Patents
A kind of arsenic-containing waste water processing unit Download PDFInfo
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- CN208136016U CN208136016U CN201820217065.5U CN201820217065U CN208136016U CN 208136016 U CN208136016 U CN 208136016U CN 201820217065 U CN201820217065 U CN 201820217065U CN 208136016 U CN208136016 U CN 208136016U
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Abstract
The utility model belongs to water pollution control correlative technology field, more specifically, it is related to a kind of arsenic-containing waste water processing unit, it includes arsenic-containing waste water oxidation processes portion and solidification treatment portion, wherein arsenic-containing waste water oxidation processes portion successively includes the grid pond connected by pipeline, rotational flow grit chamber, conditioning tank, microwave reaction pond and secondary settling tank, the device can realize the primary filtration of arsenic-containing waste water, pH is adjusted, microwave catalysis oxidation and precipitation and separation, wherein pass through the ingenious setting of wave absorbing agent plate and aerated conduit in microwave reaction pond, the fully oxidized of arsenic-containing waste water may be implemented, trivalent arsenic is set to be converted into pentavalent arsenic, and it is co-precipitated with ferric iron, arsenic-containing waste water after obtaining microwave treatment and the sludge containing ferric arsenate.The device is simple and easy, and treatment effeciency is high, easy to industrialized production.
Description
Technical field
The utility model belongs to water pollution control correlative technology field, more particularly, to a kind of processing of arsenic-containing waste water
Device.
Background technique
With the rapid development of industry, water body arsenic (As) pollution problem is more and more serious, to ecological environment and human health
Very big harm is brought, has become question of common concern at present.Arsenic is located at《Chinese environmental priority pollutant blacklist》In " huge sum of money
First of category and its compound ", arsenical can produce serious harm to animals and plants and human body.The discharge of Industrial " three Waste " is
The main source of arsenic in water body." three wastes " of the industries such as mining, smelting, plating, chemical industry are handling below standard or even are not being appointed
In the case where is managed, directly or indirectly it is discharged into environment and causes water body arsenic pollution.China is that water body arsenic pollution is the tightest
One of the country of weight, population of exposure is up to 20,000,000, and the ground such as Taiwan, Hunan, Guangdong, Xinjiang, Shanxi and Inner Mongol are arsenic pollutions
Serious area.The trend for concentrating outburst is presented in surface water body arsenic pollution in China's in recent years.2014, shimen Hunan river water arsenic content was super
More than 1000 times are marked, there are half people's arsenic poisoning, the grain substantially underproduction in the Heshan village in downstream, and local resident's life is severely impacted.
Body of groundwater arsenic pollution situation also very severe, threatens the drinking water safety of the mankind.It is exposed to Arsenic in Drinking Water concentration at present
The size of population greater than 50 μ g/L is up to 5,600,000, and being exposed to population of the arsenic concentration greater than 10 μ g/L is 14,660,000.Shanxi Shanyin County
Arsenic from underwater concentration reaches as high as 1530 μ g/L.Maximum arsenic concentration is up to 80 μ g/L in Northern Part of Zhejiang underground water.
The arsenic-containing waste water processing unit of the prior art there are low efficiency, it is at high cost, generate secondary pollution and be difficult to mineralising
The defect of heavy metal etc..
Utility model content
Aiming at the above defects or improvement requirements of the prior art, the utility model provides a kind of processing dress of arsenic-containing waste water
The characteristics of setting, sufficiently combining arsenic-containing waste water processing unit and demand, specific aim set arsenic-containing waste water processing unit again
Meter correspondingly achieves a kind of at low cost, high-efficient arsenic-containing waste water processing unit, thus solves the useless containing arsenic of the prior art
Low efficiency in water treatment facilities, the at high cost, technical problem that generates secondary pollution and be difficult to mineralising heavy metal etc..
To achieve the above object, according to the one aspect of the utility model, a kind of arsenic-containing waste water processing unit is provided, is wrapped
Wastewater oxidation processing unit and solidification treatment portion are included, wherein：
The wastewater oxidation processing unit includes microwave reaction pond；The microwave reaction pond includes microwave reaction pond entrance, inhales
Wave agent plate is aerated tube inlet, aeration tube, aeration tube outlet, microwave generator and exports with microwave reaction pond；The microwave is anti-
Ying Chi is used to carry out arsenic-containing waste water microwave catalysis oxidation processing, and the wave absorbing agent plate is several, is alternately disposed at described
On two opposite sides of microwave reaction pond, the wave absorbing agent plate surface load has microwave catalyst；The aeration tube entrance
It is set to microwave reaction pond top-side, for being passed through oxygen-containing gas inside the microwave reaction pond；The aeration tube
Including several I-shaped aeration tubes, the I-shaped aeration tube and the wave absorbing agent plate are arranged alternately；The arsenic-containing waste water
Under the action of the microwave catalyst and the oxygen-containing gas, catalytic oxidation occurs, trivalent arsenic is made to be converted into pentavalent arsenic,
And be co-precipitated with ferric iron, the arsenic-containing waste water, which exports after the microwave reaction pond is handled from the microwave reaction pond, to flow out.
Preferably, the wastewater oxidation processing unit further includes grid pond, rotational flow grit chamber, conditioning tank and secondary settling tank；
The grid pond includes grid pond entrance and grid pond outlet；The grid pond is used to carry out arsenic-containing waste water preliminary
Filtration treatment, arsenic-containing waste water enters the grid pond from grid pond entrance, after filtration treatment, from the grid pond outlet stream
Out；
The rotational flow grit chamber include rotational flow grit chamber entrance and rotational flow grit chamber outlet, the rotational flow grit chamber entrance with
The grid pond outlet is connected, and the rotational flow grit chamber is used to remove the grains of sand in arsenic-containing waste water；
The conditioning tank includes conditioning tank entrance, pH adjusting agent dosing mouth, blender and outlet of regulating reservoir；The eddy flow is heavy
The outlet of sand pond is connected with the conditioning tank entrance, and the pH adjusting agent dosing mouth is used to that pH to be added to the conditioning tank and adjusts
Agent, under the action of blender, the conditioning tank by the pH of the arsenic-containing waste water be adjusted to 10 hereinafter, the arsenic-containing waste water from tune
Save pond outlet outflow；
The outlet of regulating reservoir is connected with microwave reaction pond entrance, and the arsenic-containing waste water is through the microwave reaction pond
It exports and flows out from the microwave reaction pond after processing；The dreg containing arsenic that microwave reaction obtains simultaneously is under oxygen-containing gas effect, gas
Float on institute's arsenic-containing waste water surface layer, and enters the secondary settling tank with water flow；
The secondary settling tank includes secondary settling tank entrance, secondary settling tank outlet and mud discharging mouth, microwave reaction pond outlet with it is described
Secondary settling tank entrance is connected, and for the secondary settling tank for being separated by solid-liquid separation to the arsenic-containing waste water, it is useless containing arsenic to obtain that treated
Water and dreg containing arsenic, treated the arsenic-containing waste water is exported from the secondary settling tank to flow out, and the dreg containing arsenic is from the spoil disposal
Mouth discharge.
Preferably, the wave absorbing agent plate, which is laid staggeredly, is parallel to arsenic-containing waste water disengaging direction in the microwave reaction pond
On two opposite sides, make it is handled arsenic-containing waste water is S-type flows through the microwave reaction pond, effectively increase arsenic-containing waste water micro-
Residence time in wave reaction tank.
Preferably, the adjacent wave absorbing agent plate 0.1~1m of interval.
Preferably, the microwave reactor work when microwave frequency be 300~300000MHz, microwave power be 1~
20kW, microwave reaction time are 0.5~40min.
Preferably, the aeration tube specifically includes first level aeration tube, vertical aeration tube and the second horizontal aeration pipe；Institute
Aeration tube inlet connection first level aeration tube is stated, the first level aeration tube shunts several vertical aerations vertically downward
Pipe, each vertical aeration tube are vertical simultaneously with top first level aeration tube and vertical aeration tube in bottom reconnection one
Second horizontal aeration pipe is layed in microwave reaction bottom of pond portion, and the second horizontal aeration pipe surface opens up stomata, oxygen-containing convenient for allowing
Gas is flowed out out of pipeline, while providing oxidizing atmosphere for arsenic-containing waste water, is also risen to the sludge containing ferric arsenate that reaction generates
It is acted on to air bearing, is allowed to enter secondary settling tank with the water flow outflow of aqueous waste water.
Preferably, described device further includes solidification treatment portion, and the solidification treatment portion includes that sludge oxidation is steady
Fixed makeup is set and sludge immobilization device.It is collected into the sludge oxidative stabilization device, adds containing arsenic sludge by described
Sludge is stable agent, stirs evenly, and conserves 0.1~2 day, keeps ferric arsenate more stable, or be converted into calcium arsenate, while described in adjusting
Sludge pH 5~12 makes the sludge stabilizing；Stabilized sludge is placed in sludge immobilization equipment, adding cement makes institute
State sludge immobilization.
In general, it can obtain down the above technical solutions conceived by the present invention are compared with the prior art,
Column beneficial effect：
1, the utility model provides a kind of processing unit of arsenic-containing waste water comprising arsenic-containing waste water oxidation processes portion and dirt
Mud curing process portion, wherein arsenic-containing waste water oxidation processes portion successively include by pipeline connect fine fack and rotational flow grit chamber,
Conditioning tank, microwave reaction pond and secondary settling tank, the device can realize the primary filtration of arsenic-containing waste water, pH adjusting, microwave catalysis oxidation
And precipitation and separation, wherein pass through the ingenious setting of wave absorbing agent plate and aerated conduit in microwave reaction pond, may be implemented containing arsenic
Waste water it is fully oxidized, so that trivalent arsenic is converted into pentavalent arsenic, and be co-precipitated with ferric iron, the arsenic-containing waste water after obtaining microwave treatment
With the sludge containing ferric arsenate.The device is simple and easy, and treatment effeciency is high, easy to industrialized production.
2, the wave absorbing agent plate in the microwave reaction pond in the utility model arsenic-containing waste water processing unit is in microwave reaction pond
It is staggered on two opposite sides, makes arsenic-containing waste water is S-type to flow through microwave reaction pond, effectively increase arsenic-containing waste water in microwave
Residence time in reaction tank, and come into full contact with microwave absorption；And the wave absorbing agent plate can be recycled.
3, the aerated conduit in the utility model arsenic-containing waste water processing unit in microwave reaction pond is " I " fonts setting, is exposed
On the one hand the oxygen-containing gas that device of air provides provides the oxidant that arsenic-containing waste water catalysis oxidation needs, on the other hand also function to air bearing
Effect, make sludge when bottom aeration tube is persistently aerated, air bearing is in handled waste water surface layer, and it is heavy with water flow to enter two
Pond makes sludge settling and is collected.
4, the utility model is containing aerator in arsenic abolishment processing unit by several " I " fonts aeration tubes and several
Wave absorbing agent plate is arranged alternately, and is conducive to improve being uniformly distributed for oxygen-containing gas and microwave catalyst, convenient for arsenic-containing waste water
Homogeneous reaction improves the reaction efficiency of whole arsenic-containing waste water.
Detailed description of the invention
Fig. 1 is arsenic-containing waste water oxidation processes part device figure in the arsenic-containing waste water processing unit of the utility model；
Fig. 2 is the top view in the microwave reaction pond in the utility model arsenic-containing waste water processing unit；
Fig. 3 is that the arsenic-containing waste water in the microwave reaction pond in the utility model arsenic-containing waste water processing unit flows to top view；
Fig. 4 is the device figure of aeration tube in the utility model arsenic-containing waste water processing unit；
Fig. 5 is the utility model arsenic-containing waste water processing technological flow figure.
In all the appended drawings, identical appended drawing reference is used to denote the same element or structure, wherein：
1- grid pond, 11- grid pond entrance, the outlet of 12- grid pond, 2- rotational flow grit chamber, 21- rotational flow grit chamber entrance,
The outlet of 22- rotational flow grit chamber, 3- conditioning tank, 31- conditioning tank entrance, 32-pH regulator dosing mouth, 33- blender, 34- are adjusted
Pond outlet, 4- microwave reaction pond, 41- microwave reaction pond entrance, 42- wave absorbing agent plate, 43- aeration tube inlet, 44- aeration tube,
441- first level aeration tube；The vertical aeration tube of 442-；The second horizontal aeration of 443- pipe, the outlet of 45- aeration tube, 46- microwave hair
Raw device, the outlet of 47- microwave reaction pond, 5- secondary settling tank, 51- secondary settling tank entrance, the outlet of 52- secondary settling tank, 53- mud discharging mouth.
Specific embodiment
In order to make the purpose of the utility model, technical solutions and advantages more clearly understood, below in conjunction with attached drawing and implementation
Example, the present invention will be further described in detail.It should be appreciated that specific embodiment described herein is only used to explain
The utility model is not used to limit the utility model.In addition, institute in the various embodiments of the present invention described below
The technical characteristic being related to can be combined with each other as long as they do not conflict with each other.
The utility model provides a kind of arsenic-containing waste water processing unit, including wastewater oxidation processing unit and solidification treatment
Portion, wherein：Wastewater oxidation processing unit includes grid pond 1, rotational flow grit chamber 2, conditioning tank 3, microwave reaction pond 4 and secondary settling tank 5.
Grid pond 1 includes grid pond entrance 11 and grid pond outlet 12；Grid pond 1 is used to carry out preliminary mistake to arsenic-containing waste water
Filter processing, arsenic-containing waste water enters grid pond 1 from grid pond entrance 11, after filtration treatment, from 12 outflow of grid pond outlet.
Rotational flow grit chamber 2 includes rotational flow grit chamber entrance 21 and rotational flow grit chamber outlet 22, and grid pond exports 12 and eddy flow
Setting pot entrance 21 is connected, and rotational flow grit chamber 2 is used to remove the grains of sand in arsenic-containing waste water.
Conditioning tank 3 includes conditioning tank entrance 31, pH adjusting agent dosing mouth 32, blender 33 and outlet of regulating reservoir 34；Eddy flow
Setting pot outlet 22 is connected with conditioning tank entrance 31, and pH adjusting agent dosing mouth 32 is used to that pH adjusting agent to be added to conditioning tank 3,
Under the action of blender 33, the pH of arsenic-containing waste water is adjusted to 10 hereinafter, arsenic-containing waste water is flowed from outlet of regulating reservoir 34 by conditioning tank 3
Out.For the dreg containing arsenic that microwave reaction obtains under oxygen-containing gas effect, air bearing enters institute in institute's arsenic-containing waste water surface layer, and with water flow
State secondary settling tank 5；Load has the wave absorbing agent plate of microwave catalyst that should replace in time in microwave reaction pond 4, recycles the suction wave of failure
Agent plate simultaneously loads the microwave catalysts such as Zero-valent Iron again, is recycled.
Microwave reaction pond 4 includes microwave reaction pond entrance 41, wave absorbing agent plate 42, aeration tube inlet 43, aeration tube 44, exposes
Tracheae outlet 45, microwave generator 46 and microwave reaction pond outlet 47；Outlet of regulating reservoir 34 is connected with microwave reaction pond entrance 41
Logical, wave absorbing agent plate 42 is the plate of several rectangles, and wave absorbing agent plate 42 is alternately disposed at opposite two in microwave reaction pond 4
On side, specially it is parallel on opposite two side in arsenic-containing waste water disengaging direction, in this way from microwave reaction bottom of pond portion
The arsenic-containing waste water that entrance enters glide path in microwave reaction pond is S-type, can sufficiently extend arsenic-containing waste water in microwave reaction
Residence time in pond, to increase its catalytic oxidation efficiency.In addition, adjacent wave absorbing agent plate 42 be spaced 0.1~1m be compared with
It is good.The catalytic oxidation that 42 area load of wave absorbing agent plate has Zero-valent Iron to participate in arsenic-containing waste water as microwave catalyst, aeration
Tube inlet 43 is set to 4 top-side of microwave reaction pond, for being passed through oxygen-containing gas inside microwave reaction pond 4；Arsenic-containing waste water
Under the action of microwave catalyst and oxygen-containing gas, catalytic oxidation occurs, trivalent arsenic is made to be converted into pentavalent arsenic, and and trivalent
Iron co-precipitation, arsenic-containing waste water is after microwave reaction pond 4 is handled from 47 outflow of microwave reaction pond outlet；Microwave reaction obtains simultaneously
For dreg containing arsenic under oxygen-containing gas effect, air bearing enters secondary settling tank 5 in institute's arsenic-containing waste water surface layer, and with water flow.Aeration tube 44 wraps
Several I-shaped aeration tubes are included, I-shaped aeration tube and wave absorbing agent plate 42 are arranged alternately, to improve W-response system
Uniformity, being uniformly distributed including gas and catalyst improve reaction efficiency.Microwave reactor 4 work when microwave frequency be
915MHz and 2450MHz, microwave power is 1~20kW, and the microwave reaction time is 0.5~40min.Microwave generator 46 is arranged
In in the microwave reaction pond 4, for microwave needed for providing reaction；Microwave generator 46 is uniformly distributed in the microwave reaction
On multiple sides in pond 4, can more evenly provide microwave source in this way, the microwave generator 46 being arranged on each side by 1~
10 magnetrons are connected in series.Air pipe inlet 43 is anti-into microwave as shown in figure 4, oxygen-containing gas exposes oneself for 44 specific structure of aeration tube
Pond 4 is answered, top first level aeration tube 441 shunts several vertical aerations being arranged alternately with wave absorbing agent plate 42 vertically downward
Pipe 442, each vertical aeration tube 442 reconnect one and top first level aeration tube 441 and vertical aeration tube in bottom
442 the second vertical simultaneously horizontal aeration pipes 443, are layed in microwave reaction bottom of pond portion, 443 surface of the second horizontal aeration pipe opens up
Stomata while providing oxidizing atmosphere for arsenic-containing waste water, also contains reaction generation convenient for allowing oxygen-containing gas to flow out out of pipeline
The sludge of ferric arsenate plays the role of air bearing, is allowed to enter secondary settling tank 5 with the water flow outflow of aqueous waste water.Remaining oxygen-containing gas exposes oneself
45 discharge of tracheae outlet.
Secondary settling tank 5 includes secondary settling tank entrance 51, secondary settling tank outlet 52 and mud discharging mouth 53, and microwave reaction pond outlet 47 and two is heavy
Pond entrance 51 is connected, and secondary settling tank 5 is for being separated by solid-liquid separation arsenic-containing waste water, the arsenic-containing waste water that obtains that treated and dirty containing arsenic
Mud, treated, and arsenic-containing waste water is flowed out from secondary settling tank outlet 52, and dreg containing arsenic is discharged from mud discharging mouth 53.
The device further includes solidification treatment portion, and solidification treatment portion includes sludge oxidative stabilization device and sludge
Immobilization device.It will be collected into the sludge oxidative stabilization device containing arsenic sludge, and add sludge is stable agent, stirring is equal
It is even, it conserves 0.1~2 day, keeps ferric arsenate more stable, or be converted into calcium arsenate, while adjusting the sludge pH 5~12, make institute
State sludge stabilizing；Stabilized sludge is placed in sludge immobilization equipment, adding cement makes sludge immobilization.
The processing that arsenic-containing waste water is carried out using above-mentioned apparatus, is included the following steps：
(1) arsenic-containing waste water is filtered, removes and adjusts pH to 10 again after suspended particulate substance hereinafter, it is preferred that 1~8, it is excellent
Recruiting and saving the pH of arsenic-containing waste water is 2~6；
(2) microwave catalysis oxidation precipitation process, microwave frequency are carried out in oxygen-containing atmosphere to step (1) described arsenic-containing waste water
For 300-300000MHz, microwave power is 5~20kW, and the microwave reaction time is 4~40min；Trivalent arsenic is set to be converted into pentavalent
Arsenic, and be co-precipitated with ferric iron, the arsenic-containing waste water after obtaining microwave treatment and the sludge containing ferric arsenate, it is useless after microwave treatment
Water or qualified discharge, or return and handled again in initial waste pond, until qualified discharge.Microwave power is preferably 20kW, microwave
React 30min.
Wherein, microwave catalyst is negative the suction wave substance of Zero-valent iron-carrying, and the relative dielectric constant for inhaling wave substance is not low
In 4, such as silicon carbide, active carbon, charcoal, ferrite, graphite, carbon black, iron mineral or manganese mineral.The suction wave substance is in this reality
It is the absorbing property for improving Zero-valent Iron with novel effect.It is practical as this when using different suction wave substances and loading Zero-valent Iron
When novel microwave catalyst, the mode of specific load preparation is different, for example, using the silicon carbide of Zero-valent Iron load as microwave
When catalyst, which can be prepared by the method for electro-deposition, and silicon carbide is tubulose, rodlike or plate.With iron
Piece is anode, using silicon carbide as cathode, using ferrous salt as electrolyte, is 0.5~2A in constant current, is powered after 10~40min
Obtain it is described load Zero-valent Iron silicon carbide microwave catalyst, ferrous salt be ferrous sulfate, ferrous nitrate it is one or more.Its
Preparation method specifically includes following steps：
(1) be carbonized silica purge：Using deionized water by after silicon carbide cleaning 3~10 times, be placed in 0.5~5% hydrochloric acid or
Ultrasound 30min in nitric acid or sulfuric acid solution, then takes out and is cleaned 3~10 times with deionized water, is placed in electric drying oven with forced convection
8h is dried at 105 DEG C, is taken out, is cooled to room temperature, it is spare.(2) Zero-valent Iron loads：0.01~0.1mol ferrous salt is dissolved in
In 100~500mL deionized water, a little sulfuric acid or nitric acid is added, prevents Fe2+It is oxidized, prepares 0.05~0.20mol L–1's
Corresponding iron salt solutions are electrolyte.Electro-deposition is carried out with D.C. regulated power supply, is with the purified silicon carbide in step (1)
Cathode, iron plate are anode, and constant current is 0.5~2A, and Zero-valent Iron load silicon carbide microwave is obtained after the 10~40min that is powered and is urged
Agent.
When microwave catalyst using Zero-valent Iron load type active carbon as the utility model, the suction of Zero-valent Iron can also be improved
Wave performance can be prepared by liquid phase reduction.Compared with the silicon carbide microwave catalyst of Zero-valent Iron load, Zero-valent Iron is negative
The active carbon of load and zeroth order iron-binding capacity are strong, are not easy to secondary use, need to consume a large amount of acid solution elution when reusing, and
And active carbon in sewage organic pollutant and heavy metal include trivalent arsenic ion have certain adsorptivity, once absorption
It is not easy to immobilization disposition；Comparatively, the microwave catalyst using Zero-valent Iron load silicon carbide as the utility model, function
There can be specificity, absorbing property is excellent, can greatly enhance the absorbing property of Zero-valent Iron, and it can very easily be recycled
It recycles, is rinsed only by simple water.And silicon carbide can be made tubulose, rodlike or plate, and it can also be micro-
Special arrangement form is used in wave reactor, is conducive to the laying and recycling and reusing of silicon carbide microwave absorption.
(3) sludge described in step (2) containing ferric arsenate is subjected to stabilization processes, i.e., adds sludge into the sludge
Stabilizer calcium oxide or/and calcium hypochlorite make ferric arsenate be converted into calcium arsenate, while adjusting the sludge pH, keep the sludge steady
Fixedization simultaneously reaches standard of landfill.
High-level oxidation technology (Advanced Oxidation Processes, AOPs) be with generate hydroxyl radical free radical (
OH) for mark, using generation OH oxidation water body in pollutant and reach removal pollutant processing technique, have oxidation
The feature that ability is strong, treatment effeciency is high.Traditional high-level oxidation technology is with H2O2For oxidant, processing cost is high, and high concentration H2O2
It is unstable, it makes troubles to storage and transport, it is difficult to be applied in Practical Project.With O2For the activate molecular oxygen technology of oxidant
Because its is low in cost, strong operability, it is without secondary pollution due to be widely studied and applied.Activate molecular oxygen technology, which mainly passes through, urges
Agent is by oxygen activating generation active specy OH, O of molecular state2 -And H2O2, As (III) in oxidable water.
Micro ware auxiliary catalysis oxidation technology is as a kind of novel wastewater processing technology, because having rapidly and efficiently heating, heat
Source is not directly contacted with medium, selectivity heating, easily controllable, the advantages that being generated without waste and receive significant attention.By microwave
The treatment effeciency that can be improved organic wastewater with difficult degradation thereby with the combination of other oxidation technologies, adds some microwave catalysts in processes
The processing speed of waste water can more be accelerated.Micro ware auxiliary catalysis oxidation is used for and Fenton oxidation method (Fe2++H2O2) combine, it is real
The degradation and mineralising of existing pollutant, but it is limited to the absorbability of microwave.Activate molecular oxygen technology is Fenton oxygen at this stage
The research hotspot of change method, wherein nano zero valence iron (Fe0) can degradation and a huge sum of money of the effective activation molecular oxygen for Organic substance in water
The removal of category.But nano zero valence iron is easy to happen reunion because of its large specific surface area, its reactivity is caused to substantially reduce.
The utility model it has been found that no microwave participate in the case where, fail the oxygen for detecting As (III)
Change.The method for treating arsenic-containing wastewater of the utility model passes through the organic contamination in micro ware auxiliary catalysis oxidation technology degrading waste water
Object, while effectively can also convert pentavalent arsenic for the trivalent arsenic in waste water and be co-precipitated to form arsenic acid eventually by with ferric iron
Iron precipitating sludge is to remove.The micro ware auxiliary catalysis oxidation technology of the utility model is without being added expensive H2O2And O3Deng
Oxidant, the directly O in energy activating air2Generate active specy (such as OH and O2 -), meanwhile, activate the activation shape of generation
State oxygen species OH and O2 -With the reactivity for being much larger than ground state molecule oxygen, As (III) fast and effeciently is aoxidized, reduces it
Toxicity.
The microwave catalyst that the utility model micro ware auxiliary catalysis oxidation technology uses is negative the silicon carbide of Zero-valent iron-carrying, and zero
Valence iron itself has certain absorbing property, and the absorbing property of silicon carbide itself is fine, and Zero-valent Iron is supported on absorbing property
High-intensitive short pulse microwave is radiated load Zero-valent Iron by the reactivity worth that Zero-valent Iron can be greatly enhanced on silicon carbide outstanding
Silicon carbide, some points are selectively quickly heated up to very high temperature and form " the heat with excitation on surface
Point " accelerates reaction；On the other hand, be conducive to the Zero-valent Iron loaded on silicon carbide and reduce reunite, Zero-valent Iron can by bielectron and
Single electron pathway activation molecular oxygen is formed with O2For the Fenton-like technology of oxidant, the oxidative degradation to organic matter is realized, from
The Fe peeled off on silicon carbide3+It can further be formed and be co-precipitated with heavy metals such as arsenic, to remove Heavy Metals in Waters.This is practical new
Suction of the type under aerobic conditions, by Zero-valent Iron and its oxide surface to the Absorptive complex wave of arsenic and the hydrous oxide of iron to arsenic
Attached co-precipitation is oxidized to As (V) along with As (III), reach higher than under oxygen free condition to the removal rate of As (III).
Under microwave irradiation, the surface Fe/SiC is brought rapidly up to be formed " hot spot ", excites Fe0Pass through bielectron and single electron approach
Activate molecular oxygen.When by bielectron approach, O2Obtain 2e–It is directly reduced to H2O2, Fe0It is oxidized to Fe2+, Fe2+With H2O2Group
It is reacted at Fenton and generates As (III) in OH oxidation water, as shown in formula (1) to (3)；When single electron approach, O2Obtain e–It is gone back
Original is at O2 –, O2 –E is obtained again–It is reduced into H2O2, OH is further generated, as shown in formula (4) to (5).The Fe of generation3+
The Fe for exposing inner layer is peeled off from SiC0Continuation activate molecular oxygen, and Fe3+Into solution and H2O reaction generates HFO, and absorption is altogether
Precipitating removes As (V) and As (III) in water removal, as shown in formula (6).
Fe0+O2+2H+→Fe2++H2O2 (1)
Fe2++H2O2→Fe3++·OH+OH- (2)
Fe0+H2O2+2H+→Fe2++H2O (3)
Fe2++O2→Fe3++·O2 - (4)
Fe2++·O2 -+H+→Fe3++H2O2 (5)
2Fe3++3H2O→2Fe(OH)3 3++3H+ (6)
The following are embodiments：
Embodiment 1
A kind of arsenic-containing waste water processing unit, as shown in Figure 1, including wastewater oxidation processing unit and solidification treatment portion,
In：Wastewater oxidation processing unit includes grid pond 1, rotational flow grit chamber 2, conditioning tank 3, microwave reaction pond 4 and secondary settling tank 5.
Grid pond 1 includes grid pond entrance 11 and grid pond outlet 12；Grid pond 1 is used to carry out preliminary mistake to arsenic-containing waste water
Filter processing, arsenic-containing waste water enters grid pond 1 from grid pond entrance 11, after filtration treatment, from 12 outflow of grid pond outlet.
Rotational flow grit chamber 2 includes rotational flow grit chamber entrance 21 and rotational flow grit chamber outlet 22, and grid pond exports 12 and eddy flow
Setting pot entrance 21 is connected, and rotational flow grit chamber 2 is used to remove the grains of sand in arsenic-containing waste water.
Conditioning tank 3 includes conditioning tank entrance 31, pH adjusting agent dosing mouth 32, blender 33 and outlet of regulating reservoir 34；Eddy flow
Setting pot outlet 22 is connected with conditioning tank entrance 31, and pH adjusting agent dosing mouth 32 is used to that pH adjusting agent to be added to conditioning tank 3,
Under the action of blender 33, the pH of arsenic-containing waste water is adjusted to 10 hereinafter, arsenic-containing waste water is flowed from outlet of regulating reservoir 34 by conditioning tank 3
Out.For the dreg containing arsenic that microwave reaction obtains under oxygen-containing gas effect, air bearing enters institute in institute's arsenic-containing waste water surface layer, and with water flow
State secondary settling tank 5；Load has the wave absorbing agent plate of microwave catalyst that should replace in time in microwave reaction pond 4, recycles the suction wave of failure
Agent plate simultaneously loads the microwave catalysts such as Zero-valent Iron again, is recycled.
As shown in Fig. 2, microwave reaction pond 4 include microwave reaction pond entrance 41, wave absorbing agent plate 42, aeration tube inlet 43,
Aeration tube 44, aeration tube outlet 45, microwave generator 46 and microwave reaction pond outlet 47；Outlet of regulating reservoir 34 and microwave reaction pond
Entrance 41 is connected, and wave absorbing agent plate 42 is the plate of several rectangles, and wave absorbing agent plate 42 is alternately disposed at microwave reaction pond 4
On two opposite sides, specially it is parallel on opposite two side in arsenic-containing waste water disengaging direction, it is anti-from microwave in this way
The arsenic-containing waste water for answering the entrance of bottom of pond portion to enter glide path in microwave reaction pond is S-type, and Fig. 3 is arsenic-containing waste water processing unit
In the arsenic-containing waste water in microwave reaction pond flow to top view, as shown in figure 3, such set-up mode can sufficiently extend it is useless containing arsenic
Residence time of the water in microwave reaction pond, to increase its catalytic oxidation efficiency.In addition, adjacent wave absorbing agent plate 42 is spaced
0.1~1m.The catalytic oxidation that 42 area load of wave absorbing agent plate has Zero-valent Iron to participate in arsenic-containing waste water as microwave catalyst,
Aeration tube inlet 43 is set to 4 top-side of microwave reaction pond, for being passed through oxygen-containing gas inside microwave reaction pond 4；Containing arsenic
In microwave catalyst and under the action of oxygen-containing gas catalytic oxidation occurs for waste water, and trivalent arsenic is made to be converted into pentavalent arsenic, and with
Ferric iron co-precipitation, arsenic-containing waste water is after microwave reaction pond 4 is handled from 47 outflow of microwave reaction pond outlet；Microwave reaction obtains simultaneously
For the dreg containing arsenic arrived under oxygen-containing gas effect, air bearing enters secondary settling tank 5 in institute's arsenic-containing waste water surface layer, and with water flow.Aeration tube
44 include several I-shaped aeration tubes, and I-shaped aeration tube and wave absorbing agent plate 42 are arranged alternately, to improve W-response body
The uniformity of system, being uniformly distributed including gas and catalyst improve reaction efficiency.Microwave generator 46 is set to the microwave
In reaction tank 4, for microwave needed for providing reaction；Microwave generator 46 is uniformly distributed more in the microwave reaction pond 4
On a side, microwave source can be more evenly provided in this way, and the microwave generator 46 being arranged on each side is by 1~10 magnetron
It is connected in series.As shown in figure 4, oxygen-containing gas exposes oneself, air pipe inlet 43 enters microwave reaction pond 4, top to 44 specific structure of aeration tube
First level aeration tube 441 shunts several vertical aeration tubes 442 being arranged alternately with wave absorbing agent plate 42 vertically downward, each
A vertical aeration tube 442 is vertical simultaneously with top first level aeration tube 441 and vertical aeration tube 442 in bottom reconnection one
The second horizontal aeration pipe 443, be layed in microwave reaction bottom of pond portion, 443 surface of the second horizontal aeration pipe opens up stomata, convenient for allowing
Oxygen-containing gas is flowed out out of pipeline, while providing oxidizing atmosphere for arsenic-containing waste water, also to the dirt containing ferric arsenate of reaction generation
Mud plays the role of air bearing, is allowed to enter secondary settling tank 5 with the water flow outflow of aqueous waste water.Remaining oxygen-containing gas exports 45 from aeration tube
Discharge.
Secondary settling tank 5 includes secondary settling tank entrance 51, secondary settling tank outlet 52 and mud discharging mouth 53, and microwave reaction pond outlet 47 and two is heavy
Pond entrance 51 is connected, and secondary settling tank 5 is for being separated by solid-liquid separation arsenic-containing waste water, the arsenic-containing waste water that obtains that treated and dirty containing arsenic
Mud, treated, and arsenic-containing waste water is flowed out from secondary settling tank outlet 52, and dreg containing arsenic is discharged from mud discharging mouth 53.
The device further includes solidification treatment portion, the solidification treatment portion include sludge oxidative stabilization device and
Sludge immobilization device.It is collected into described in the sludge oxidative stabilization device containing arsenic sludge, adds sludge is stable agent,
Stir evenly, conserve 0.1~2 day, keep ferric arsenate more stable, or be converted into calcium arsenate, at the same adjust the sludge pH 5~
12, make the sludge stabilizing；Stabilized sludge is placed in sludge immobilization equipment, adding cement fixes the sludge
Change.It is as shown in Figure 5 that the utility model handles arsenic-containing waste water process flow chart.
The processing that arsenic-containing waste water is carried out using above-mentioned apparatus, is included the following steps：
(1) preparation of microwave catalyst：After cleaning SiC 5 times using deionized water, it is placed in 1% H2SO4Surpass in solution
Sound 30min then takes out and is cleaned 5 times with deionized water, is placed in electric drying oven with forced convection at 105 DEG C and dries 8h, takes out, cold
But spare to room temperature.Then by 11.12gFeSO4·7H2O is dissolved in 200mL deionized water, and a little H is added2SO4Prevent Fe2+
It is oxidized, prepares the FeSO of 0.20mol/L4Solution is electrolyte.Electro-deposition is carried out with D.C. regulated power supply, with pretreated
SiC is cathode, and bright iron plate is anode, obtains Fe/SiC after constant current 1.00A, energization 20min.
(2) wastewater oxidation precipitates：
20mg/L arsenic-containing waste water is concentrated on into former pond, the water in raw water slot is introduced into fine fack and rotational flow grit chamber
In, after filtering suspended particulate substance, it is introduced into conditioning tank and acid-base modifier is added, after being adjusted to 5, drawn waste water by pipeline
Enter into microwave reactor i.e. microwave reaction pond, selection microwave frequency is 915MHz, and adjustment microwave power is that 20kW carries out microwave
Oxidation precipitation is handled, and air is continually fed into before microwave reaction, and in microwave catalyst presence, microwave reaction 30min.Reaction
Afterwards, it is passed through in secondary settling tank and is separated by solid-liquid separation, after sampling, detect that water outlet arsenic concentration is 0.1mg/L, arsenic removal using ICP-OES
Rate is up to 99.5%.
(3) sludge is stable immobilization：
The sludge generated after microwave reaction is collected into sludge oxidative stabilization device, adds 5% hypochlorous acid first
Calcium stirs evenly, and adds 5% calcium oxide.Maintenance 0.1~2 day realizes and stabilizes that the leachate pH after stabilisation is 11.
It is As (V) in conjunction with the characteristic peak that can be 45.3eV in XPS interpretation of result, is in conjunction with the characteristic peak that can be 44.1eV
As (III), and As (V):As (III)=1:1.16, illustrate under microwave irradiation, Zero-valent Iron activate molecular oxygen generates active specy
As in water (III) is aoxidized, iron (hydrogen) oxide of generation is acted on by adsorption coprecipitation removes it from water.Meanwhile HCl
As (V) in treated sample:As (III)=1:1.22, oxygenation efficiency 43.5% illustrates after being reacted with HCl dissolution in system
Iron and its compound, by the arsenic in conjunction with iron be discharged into solution have feasibility.Calcium hypochlorite dreg containing arsenic before and after the processing
XRD diagram spectrum analysis it is found that As is mainly As (III) in primary sludge, there is As (III) characteristic peak in 44.2eV, account for total
There is As (V) characteristic peak in 45.2eV in 90% or more of As.(Ca/As molar ratio is 2.0) after 5% calcium hypochlorite is handled is added,
The ratio of As (III) is reduced to 55% in sludge, and the ratio of As (V) is increased to 45% from 10%, illustrates calcium hypochlorite by As
(III) partial oxidation is As (V).
Embodiment 2
The processing that arsenic-containing waste water is carried out using arsenic-containing waste water processing unit described in embodiment 1, is included the following steps：
(1) preparation of microwave catalyst：After being cleaned SiC 3 times using deionized water, it is placed in 1% HCl solution ultrasonic
30min then takes out and is cleaned 3 times with deionized water, is placed in electric drying oven with forced convection at 105 DEG C and dries 8h, takes out, cooling
It is spare to room temperature.Then by 11.12gFeSO4·7H2O is dissolved in 200mL deionized water, and a little H is added2SO4Prevent Fe2+Quilt
Oxidation, prepares the FeSO of 0.20mol/L4Solution is electrolyte.Electro-deposition is carried out with D.C. regulated power supply, with pretreated
SiC is cathode, and bright iron plate is anode, obtains Fe/SiC after constant current 1.00A, energization 20min.
(2) wastewater oxidation precipitates：
10mg/L arsenic-containing waste water is concentrated on into former pond, the water in raw water slot is introduced into fine fack and rotational flow grit chamber
In, after filtering suspended particulate substance, it is introduced into conditioning tank and acid-base modifier is added, after being adjusted to 5, drawn waste water by pipeline
Enter into microwave reactor i.e. microwave reaction pond, selection microwave frequency is 915MHz, and adjustment microwave power is that 20kW carries out microwave
Oxidation precipitation is handled, and is continually fed into air before microwave reaction, and launch microwave catalyst.Microwave reaction 30min.After reaction, lead to
Enter in secondary settling tank and be separated by solid-liquid separation, after sampling, detects that water outlet arsenic concentration is 0.1mg/L using ICP-OES, arsenic removal rate reaches
99%.
(3) sludge is stable immobilization：
The sludge generated after microwave reaction is collected into, in sludge oxidative stabilization device, adds 10% sulfuric acid first
Ferrous iron stirs evenly, and adds 5% calcium oxide.Maintenance 0.1~2 day realizes and stabilizes that the leachate pH after stabilisation is
7。
Embodiment 3
The processing that arsenic-containing waste water is carried out using arsenic-containing waste water processing unit described in embodiment 1, is included the following steps：
(1) preparation of microwave catalyst：After being cleaned active carbon 3 times using deionized water, it is placed in 1% HCl solution
Ultrasonic 30min then takes out and is cleaned 3 times with deionized water, is placed in electric drying oven with forced convection at 105 DEG C and dries 8h, takes out,
It is cooled to room temperature, it is spare.Ferrous salt solid is dissolved into dehydrated alcohol and deoxidation deionized water mixed solution, it in proportion will be sub-
Ferrous solution is added in purified active carbon, obtain mixed liquor and stir 6~for 24 hours so that ferrous ion be sufficiently adsorbed onto it is glutinous
On native mineral.Then mixture is centrifugated, is respectively washed 1~3 time using dehydrated alcohol and deoxidation deionization.Then by solid phase
Mixture re-dissolves into dehydrated alcohol-deoxidation deionized water mixed solution, adds dropwise in proportion under lasting stirring condition
Enter~2M sodium borohydride or solution of potassium borohydride, is passed through nitrogen therebetween or argon gas carries out anoxybiotic protection, continue after dripping
After stirring 2~8h, it is separated by solid-liquid separation, then with washes of absolute alcohol 1~5 time, finally obtained sediment is being dried in vacuo
In case dry 6 under the conditions of 40~70 DEG C~for 24 hours, Zero-valent Iron load type active carbon can be prepared.
(2) 18mg/L arsenic-containing waste water is concentrated on into former pond, the water in raw water slot is introduced into fine fack and sediment by rotational flow
Chi Zhong is introduced into conditioning tank and acid-base modifier is added after filtering suspended particulate substance, after being adjusted to 5, by pipeline by waste water
It is introduced into microwave reactor i.e. microwave reaction pond, selection microwave frequency is 915MHz, and adjustment microwave power is that 20kW progress is micro-
Wave oxidation precipitation is handled, and is continually fed into air before microwave reaction, and launch microwave catalyst.Microwave reaction 30min.After reaction,
It is passed through in secondary settling tank and is separated by solid-liquid separation, after sampling, detect that water outlet arsenic concentration is 0.1mg/L using ICP-OES, arsenic removal rate reaches
99.4%.
As it will be easily appreciated by one skilled in the art that the above is only the preferred embodiment of the utility model only, not
To limit the utility model, any modification made within the spirit and principle of the present invention, equivalent replacement and change
Into etc., it should be included within the scope of protection of this utility model.
Claims (5)
1. a kind of arsenic-containing waste water processing unit, which is characterized in that including wastewater oxidation processing unit and solidification treatment portion；Its
In：
The wastewater oxidation processing unit includes microwave reaction pond (4)；The microwave reaction pond (4) includes microwave reaction pond entrance
(41), wave absorbing agent plate (42), aeration tube inlet (43), aeration tube (44), aeration tube outlet (45), microwave generator (46) and
Microwave reaction pond exports (47)；The microwave reaction pond (4) is used to carry out microwave catalysis oxidation processing to arsenic-containing waste water；The suction
Wave agent plate (42) is several, is alternately disposed on two opposite sides of the microwave reaction pond (4), the wave absorbing agent plate
Material (42) area load has microwave catalyst；The aeration tube entrance (43) is set to microwave reaction pond (4) top-side,
For being passed through oxygen-containing gas to the microwave reaction pond (4) is internal；The aeration tube (44) includes several I-shaped aeration tubes,
The I-shaped aeration tube and the wave absorbing agent plate (42) are arranged alternately；The arsenic-containing waste water is through the microwave reaction pond (4)
It is flowed out after processing from microwave reaction pond outlet (47).
2. arsenic-containing waste water processing unit as described in claim 1, which is characterized in that the wastewater oxidation processing unit further includes lattice
Grid pond (1), rotational flow grit chamber (2), conditioning tank (3) and secondary settling tank (5)；
The grid pond (1) includes grid pond entrance (11) and grid pond outlet (12)；The grid pond (1) is used for useless containing arsenic
Water carries out primary filtration processing, and arsenic-containing waste water enters the grid pond (1) from grid pond entrance (11), after filtration treatment, from
Grid pond outlet (12) outflow；
The rotational flow grit chamber (2) includes rotational flow grit chamber entrance (21) and rotational flow grit chamber outlet (22), the sediment by rotational flow
Pond entrance (21) is connected with grid pond outlet (12), and the rotational flow grit chamber (2) is used to remove the sand in arsenic-containing waste water
Grain；
The conditioning tank (3) includes conditioning tank entrance (31), pH adjusting agent dosing mouth (32), blender (33) and outlet of regulating reservoir
(34)；The rotational flow grit chamber outlet (22) is connected with the conditioning tank entrance (31), the pH adjusting agent dosing mouth (32)
For pH adjusting agent to be added to the conditioning tank (3), under the action of blender (33), the conditioning tank (3) described will contain arsenic
The pH of waste water is adjusted to 10 hereinafter, the arsenic-containing waste water is flowed out from outlet of regulating reservoir (34)；
The outlet of regulating reservoir (34) is connected with microwave reaction pond entrance (41)；What microwave reaction obtained simultaneously is dirty containing arsenic
For mud under oxygen-containing gas effect, air bearing enters the secondary settling tank (5) in institute's arsenic-containing waste water surface layer, and with water flow；
The secondary settling tank (5) includes secondary settling tank entrance (51), secondary settling tank outlet (52) and mud discharging mouth (53), the microwave reaction pond
Outlet (47) is connected with the secondary settling tank entrance (51), and the secondary settling tank (5) is used to carry out solid-liquid point to the arsenic-containing waste water
From, obtain that treated arsenic-containing waste water and dreg containing arsenic, described treated that arsenic-containing waste water exports (52) from the secondary settling tank flows
Out, the dreg containing arsenic is discharged from the mud discharging mouth (53).
3. device as described in claim 1, which is characterized in that the wave absorbing agent plate (42) is laid staggeredly anti-in the microwave
Ying Chi (4) is parallel on opposite two side in arsenic-containing waste water disengaging direction.
4. device as claimed in claim 3, which is characterized in that the adjacent wave absorbing agent plate (42) is spaced 0.1~1m.
5. device as described in claim 1, which is characterized in that the aeration tube (44) include first level aeration tube (441),
Vertical aeration tube (442) and the second horizontal aeration pipe (443)；The aeration tube entrance (43) connects first level aeration tube
(441), the first level aeration tube (441) shunts several vertical aeration tubes (442) vertically downward, each vertical aeration
It manages (442) and reconnects one and top first level aeration tube (441) and vertical aeration tube (442) while vertical the in bottom
Two horizontal aeration pipes (443), are layed in microwave reaction bottom of pond portion, and the second horizontal aeration pipe (443) surface opens up stomata.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143661A (en) * | 2019-05-23 | 2019-08-20 | 华中科技大学 | A method of arsenic in rich calcium high-arsenic underground water is removed with charcoal |
| CN111534332A (en) * | 2020-04-28 | 2020-08-14 | 东南大学 | Microwave-assisted chemical-looping gasification soil heavy metal restoration plant heat treatment method |
-
2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143661A (en) * | 2019-05-23 | 2019-08-20 | 华中科技大学 | A method of arsenic in rich calcium high-arsenic underground water is removed with charcoal |
| CN111534332A (en) * | 2020-04-28 | 2020-08-14 | 东南大学 | Microwave-assisted chemical-looping gasification soil heavy metal restoration plant heat treatment method |
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