CN109304108A - Micro-nano bubble generator, method and the application in dye wastewater treatment - Google Patents
Micro-nano bubble generator, method and the application in dye wastewater treatment Download PDFInfo
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- CN109304108A CN109304108A CN201710632218.2A CN201710632218A CN109304108A CN 109304108 A CN109304108 A CN 109304108A CN 201710632218 A CN201710632218 A CN 201710632218A CN 109304108 A CN109304108 A CN 109304108A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/235—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids for making foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
- B01F23/2376—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media characterised by the gas being introduced
- B01F23/23761—Aerating, i.e. introducing oxygen containing gas in liquids
- B01F23/237611—Air
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/20—Jet mixers, i.e. mixers using high-speed fluid streams
- B01F25/28—Jet mixers, i.e. mixers using high-speed fluid streams characterised by the specific design of the jet injector
- B01F25/281—Jet mixers, i.e. mixers using high-speed fluid streams characterised by the specific design of the jet injector the jet injector being of the explosive rapid expansion of supercritical solutions [RESS] or fluid injection of molecular spray [FIMS] type, i.e. the liquid is jetted in an environment (gas or liquid) by nozzles, in conditions of significant pressure drop, with the possible generation of shock waves
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/305—Treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The present invention provides a kind of generating device of micro-nano bubble, method and the application in dye wastewater treatment, micro-nano bubble generator of the present invention includes pressure air-dissolving tank, gas-liquid mixing pump, ejector and water tank.Apparatus of the present invention can produce that a large amount of rates of climb are slow, micro-nano bubble of the diameter mostly between 100nm~300nm by adjusting the inspiratory capacity of gas-liquid mixing pump and ejector.For waste water from dyestuff coloration depth, COD high, problem difficult to degrade, the oxygen-enriching of micro-nano bubble and produce hydroxyl radical free radical characteristic can organic matter in non-selectivity degradation water, and the foam generated in degradation process can be alleviated by fine adjustment temperature, salinity, anti-foam agent concentration etc..The generating device and method of micro-nano bubble provided by the invention have high application value in dye wastewater treatment.
Description
Technical field
The invention belongs to dye wastewater treatment technology field more particularly to a kind of generating devices of micro-nano bubble, method
And the application in dye wastewater treatment.
Background technique
Waste water from dyestuff is mainly the waste water generated during DYE PRODUCTION, since domestic dyes is various, production
Complex process causes in waste water from dyestuff often containing there are many organic matter and salinities.Most of dyestuff has the fragrance of macromolecule
Ring structure, this makes the organic matter in waste water from dyestuff have performance stabilization, COD high, problem difficult to degrade.
Currently, the processing technique of waste water from dyestuff mainly includes absorption method, Coagulation Method, advanced oxidation processes, biological oxidation process etc..
However, absorption method and flocculent precipitation sludge output are larger, and the higher cost of adsorbent or coagulant, and pollutant is immobilized
Into adsorbent or coagulant, degradation can not be mineralized.Advanced oxygen based on Fenton oxidation, photocatalysis, electrochemical oxidation
Change method, without selectivity, has preferable treatment effect to the waste water from dyestuff of high concentration to the degradation of pollutant.But Fenton oxidation
There may be secondary pollutions for the iron cement of generation, and Fenton reaction is more demanding to pH, and remineralization efficacy is limited；With TiO2For generation
The photochemical catalytic oxidation of table is limited to the Utilization ability of visible light；Electrochemical oxidation is industrially difficult to extensively due to higher cost
Using.Biological oxidation process is since reaction time is long, takes up a large area, moreover, being directed to this special chemical structure of dyestuff and toxicity
Substance, it is difficult to control the normal metabolic processes of microorganism in sludge, thus also have certain limitation.
It would therefore be highly desirable to develop, one kind is safe and reliable, do not generate secondary pollution, reaction time is short, reduces occupied area, is convenient for
The method of manipulation and a kind of lower-cost green processing waste water from dyestuff.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: it is generated by jet stream micro-nano
Bubble can generate the active specy (such as hydroxyl radical free radical) of a large amount of intermediate state with strong oxidizing property, while be greatly improved gas
Liquid mass transfer rate, the acid-base environment of setting and at a temperature of, can dyestuff effectively in degrading waste water；Simultaneously by impose a condition and
Substance addition solves the problems, such as that a large amount of foams of water surface generate in wastewater treatment；Wastewater treatment method is at low cost, operation is simple
Single, generation without secondary pollution avoids the influence promoted to subsequent industrial production, so as to complete the present invention.
The purpose of the present invention is to provide following technical schemes:
(1) a kind of generating device of micro-nano bubble, described device include the gas-liquid mixing pump 1 of successively piping connection, pressure
Power dissolving 2, ejector 3 and water tank 4,
Wherein, the lower end of the pressure air-dissolving tank 2 is water inlet, is connected directly with the water outlet of gas-liquid mixing pump 1, pressure
The upper end water outlet of dissolving 2 connects ejector 3；The ejector 3 generates micro-nano bubble and will contain micro-nano bubble
Fluid is passed through in water tank 4；The water inlet of the water tank 4 and gas-liquid mixing pump 1 is connected directly, and device is made to form a cyclic system
System.
(2) device according to above-mentioned (1), wherein be equipped with exhaust valve 21 at the top of the pressure air-dissolving tank 2；And/or
The outlet pipeline of the pressure air-dissolving tank 2, which is divided on two: one bye-passes i.e. branch 1, is connected with ejector 3, preferably props up
It is also connected with valve on road 1, valve, pressure gauge 5 and fluid flowmeter 6 are connected on another bye-pass, that is, branch 2.
(3) device according to claim (2), wherein adjust gas when generating micro-nano bubble using described device
Air inflow in liquid mixing pump 1 and ejector 3；
Preferably, the ratio of 2 flow of inspiratory capacity and branch of ejector 3 is set between 1:200~1:350, preferably
Between 1:250~1:300；And/or
Set gas-liquid mixing pump 12 flow of inspiratory capacity and branch ratio between 1:8~1:12, preferably 1:9~
Between 1:10.
(4) a kind of wastewater treatment equipment, micro-nano bubble described in one of the wastewater treatment equipment and claims 1 to 3
Generating device structure having the same；
The waste water is organic wastewater, preferably waste water from dyestuff, more preferably cationic dye wastewater, as methylene blue contaminates
Expect waste water.
(5) a kind of wastewater treatment method is handled by wastewater treatment equipment described in above-mentioned (4)；
Preferably, it the described method comprises the following steps:
Step 1) connects each building blocks of function in wastewater treatment equipment, forms the wastewater treatment equipment that can carry out fluid circulation；
Step 2) is passed through waste water into water tank, starts wastewater treatment equipment, carries out wastewater treatment.
(6) method according to above-mentioned (5), wherein further include adjusting in gas-liquid mixing pump 1 and ejector 3 in step 2
Air inflow；
Preferably, the ratio of 2 flow of inspiratory capacity and branch of ejector 3 is set between 1:200~1:350, preferably
Between 1:250~1:300；And/or
Set gas-liquid mixing pump 12 flow of inspiratory capacity and branch ratio between 1:8~1:12, preferably 1:9~
Between 1:10.
(7) method according to above-mentioned (5), wherein defoaming agent, the defoaming agent is added in treatment process into waste water
Selected from tributyl phosphate, organic silicon defoamer, polyether antifoam agent or polyethers compound organosilicon defoaming agent, preferably polyethers compounding has
Machine silicon defoaming agent.
(8) method according to above-mentioned (5), wherein when wastewater treatment, the pH value for controlling waste water is 2~5, preferably 3
~4.
(9) method according to above-mentioned (5), wherein when wastewater treatment, the treatment temperature for controlling waste water is 20~40
DEG C, preferably 20~30 DEG C.
(10) method according to above-mentioned (5), wherein right when treatment temperature is between 20 DEG C~40 DEG C when wastewater treatment
Answer the volumetric concentration of defoaming agent between 0.00045%~0.005%, preferably 0.00075%~0.003%.
Generating device, method and the answering in dye wastewater treatment of a kind of micro-nano bubble provided according to the present invention
With having the advantages that
(1) the generating device noise of micro-nano bubble is small, easy to operate: the gas-liquid mixing pump that generating device of the present invention uses
It can voluntarily air-breathing progress gas-liquid mixed operated the problems such as it is very big to avoid air compressor machine noise, while may cause oily pollution
As long as above regulating gas liquid ratio can continuously run, easy to use；
(2) foam is few during dye wastewater treatment, good degrading effect: the present invention by be added suitable defoaming agent, salt or
It adjusts the measures such as pH value, reaction temperature, anti-foam agent concentration and reduces floating foam volume；
Meanwhile the brokenly bubble effect of the diffusion pipeline section generation of ejector can substantially alleviate the generation of foam, extra foam
Tank body can also be discharged by the exhaust valve of pressure air-dissolving tank, therefore, micro-nano bubble is more steady during degrading waste water
It is fixed, it will not influence the generation efficiency of free radical；
(3) bubble diameter is small, and cavitation effect is good: by adjusting the inspiratory capacity of pressure air-dissolving tank and/or ejector, can get
The smaller bubble of diameter；
(4) for the diffuser of ejector there are cavitation effect, the high temperature and pressure instantaneously generated can make bubble collapse, not only have
Effect reduces the partial size of micro-nano bubble, while generating great amount of hydroxy group free radical, so that mineralising is carried out to the organic matter in water, because
This, can be carried out the degradation of waste water from dyestuff in water tank and ejector, be able to solve waste water from dyestuff coloration depth, COD high, difficult to degrade
The problem of, there is preferable application value.
Detailed description of the invention
Fig. 1 shows the structural schematic diagram of micro-nano bubble generator；
Fig. 2 shows the structural schematic diagrams of ejector；
Fig. 3 shows the size and particle diameter distribution of micro-nano bubble in embodiment 1；
Fig. 4 shows the degradation efficiency of embodiment 2 and 1~2 Methylene Blue of comparative example under the conditions of pH=3,7 and 9；
Fig. 5 shows the degradation efficiency of 3~5 Methylene Blue of embodiment at different temperatures；
Fig. 6 shows TOC removal rate of 5 Methylene Blue of embodiment at 40 DEG C；
Fig. 7 shows 6~7 Methylene Blue of embodiment respectively in 2g/L sodium sulphate and degradation effect under the conditions of without sodium sulphate
Rate；
Fig. 8 shows COD removal rate of 6 Methylene Blue of embodiment under the conditions of 2g/L sodium sulphate.
Drawing reference numeral explanation:
1- gas-liquid mixing pump；
11- vacuum table；
12- gas flowmeter I；
2- pressure air-dissolving tank；
21- exhaust valve；
3- ejector；
31- nozzle；
32- induction chamber；
33- trunnion；
34- diffuser pipe；
4- water tank；
5- pressure gauge；
6- fluid flowmeter；
7- gas flowmeter II.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
In the present invention, it should be noted that term " connection ", " installation " etc. can be interpreted broadly, for example, it may be
The mechanical connection such as loose joint, direct, is also possible to be connected by other media.For the ordinary skill in the art, may be used
To understand the meaning of these terms in the present invention according to the actual situation.
Pipe fitting consumptive material in the present invention can be interpreted broadly, as globe valve, pipe valve valve, gate valve can be used in valve；Stream
Meter can use spinner flowmeter, electronic flowmeter, gear meter etc., for the ordinary skill in the art, can
To understand the meaning of these terms in the present invention according to the actual situation.
The present inventor has found that common wastewater treatment mode in the prior art is in terms of the processing of waste water from dyestuff after study
Equal existing defects, and micro-nano bubble generation technology may generate beneficial technical effect in this regard.Wherein, micro-nano bubble
It is a kind of micro-bubble of diameter between 200nm~50 μm, has that large specific surface area, the residence time is long in water, high interface Zeta
Current potential such as generates free radicals at the advantages, is widely used in the industries such as aquaculture, beauty.
Micro-nano bubble generally passes through pressure air-dissolving method and generates: by being pressed into air into dissolving, making the gas in water be in
Hypersaturated state, then micro-nano bubble is precipitated in discharge suddenly.The pressure air-dissolving normal direction dissolving indentation generallyd use at present is empty
It needs not only generate noise and oily pollution, but also operate also more complicated using air compressor machine during gas；Meanwhile it generating
Bubble be mainly used in air-float technology, bubble diameter is relatively large (20~100 μm), is unfavorable for bubble and is stabilized and gas-liquid
Mass transfer, the effect in dye wastewater treatment are limited.Therefore, the innovative micro-nano air Bubble generating apparatus of exploitation and method, are improved
The quantity of micro-nano bubble, the performance for improving micro-nano bubble are rather important for micro-nano bubble degradation of dye waste water.
It is an aspect of the invention to provide a kind of generating device of micro-nano bubble, as shown in Figure 1, described device packet
Gas-liquid mixing pump 1, pressure air-dissolving tank 2, ejector 3 and the water tank 4 of successively piping connection are included,
Wherein, the lower end of the pressure air-dissolving tank 2 is water inlet, is connected directly with the water outlet of gas-liquid mixing pump 1, pressure
The upper end water outlet of dissolving 2 connects ejector 3；The ejector 3 generates micro-nano bubble and will contain micro-nano bubble
Fluid is passed through in water tank 4；The water inlet of the water tank 4 and gas-liquid mixing pump 1 is connected directly, and device is made to form a cyclic system
System.
In a preferred embodiment, the gas-liquid mixing pump 1 is Self-sucking gas/liquid mixing pump, to be directly sucked in
Large quantity of air is mixed with liquid, while avoiding the big noise that air compressor machine is generated to the gas supply of pressure air-dissolving tank 2, consuming electric power and greasy dirt
The disadvantages of dye.
In further preferred embodiment, it is also equipped with vacuum table 11 in the water inlet of gas-liquid mixing pump 1, with prison
Survey the suction conditions of 1 inlet of gas-liquid mixing pump and the working condition of gas-liquid mixing pump 1.
In embodiment still more preferably, the water in water tank 4 directly pours into gas-liquid mixing pump 1, gas-liquid mixing pump 1
Water is promoted in pipeline, while gas flowmeter I 12 being installed at the air entry of gas-liquid mixing pump 1, convenient for adjusting as needed
The flow of air inlet is to control the quantity of micro-nano bubble.
In embodiment still more preferably, the water inlet of gas-liquid mixing pump 1 is connected in pipeline with water tank 4 is connected to valve
Door cooperates with vacuum table 11, for controlling the negative pressure state in pressure air-dissolving tank 2.
In a preferred embodiment, in order to make gas discharge extra after gas-liquid mixed, 2 top of pressure air-dissolving tank
Exhaust valve 21 is installed.
In further preferred embodiment, when there is foaming substance in liquid, it can connect in 21 exit of exhaust valve
A hose is connect, the excessive foam of generation is drained back in water tank 4.
In a preferred embodiment, the outlet pipeline of the pressure air-dissolving tank 2 is divided into two: one bye-passes i.e. branch
It is connected with ejector 3 on road 1, is preferably also connected with valve, valve, pressure gauge 5 and liquid flow is connected on another bye-pass, that is, branch 2
Meter 6.Valve on branch 1 and/or branch 2, for adjusting the pressure and flow of branch 1 and branch 2.
In the present invention, as shown in Fig. 2, ejector 3 is the device of structure with the following functions: the ejector 3 includes
34 4 nozzle 31, induction chamber 32, trunnion 33, diffuser pipe parts, liquid are injected by nozzle 31, form negative pressure in induction chamber 32,
Gas, which is inhaled into together with liquid, enters trunnion 33；The drop of high-speed motion is mutually collided with gas in trunnion 33, gas quilt
Accelerate, dispersion；Into after 34 sections of diffuser pipe, flows decrease, pressure increases, and gas is compressed into micro-nano bubble, gas-liquid two-phase
To be sprayed containing the fluid form of micro-nano bubble.
In a preferred embodiment, gas flowmeter II 7 is installed at the induction chamber 32 of ejector 3, is convenient for basis
Need to adjust the flow of air inlet.
Relatively large, small compared to the diameter bubble of the micro-nano bubble diameter generated in the prior art using ejector,
The big bubble of dissolved oxygen, diameter generates free radicals etc. that abilities are smaller, and the application in dye wastewater treatment is limited.In order to solve this
Problem, the present inventor obtain gas by the inspiratory capacity in regulation gas-liquid mixing pump 1 and ejector 3 by further investigation discovery
Bubble is mostly the micro-nano bubble of minor diameter.
In the present invention, the ejector 3 at branch 1 plays release gas-liquid mixture and the double effect for being pressurized brokenly bubble.Jet stream
The inspiratory capacity of device 3 is excessive, since the gas of sucking is not dissolved in water, can not form more micro-nano bubbles, instead can
The bubble of 34 sections of diffuser pipe generations of impact, causes micro-nano bubble yield to be greatly reduced, and influences 1 pressure air-dissolving of gas-liquid mixing pump
Effect.Therefore, the inspiratory capacity that can suitably turn down ejector 3 improves micro-nano bubble yield.
And if the inspiratory capacity of gas-liquid mixing pump 1 is too small, the yield of micro-nano bubble is lower；The air-breathing of gas-liquid mixing pump 1
If amount is excessive, although the yield of micro-nano bubble theoretically can be improved, the solvability of air in water instead can
Decline.It is then desired to reasonably tune up the inspiratory capacity of gas-liquid mixing pump 1, the relationship between bubble diameter and number of bubbles is balanced.
Therefore, in the present invention, the ratio of ejector inspiratory capacity and 2 flow of branch is set between 1:200~1:350,
It is preferred that between 1:250~1:300；
Set gas-liquid mixing pump 12 flow of inspiratory capacity and branch ratio between 1:8~1:12, preferably 1:9~
Between 1:10, at this point, the micro-nano bubble diameter effect generated is best.
Micro-nano bubble generator of the present invention can generate nanometer gas of the diameter mostly between 100~300nm
Bubble, the bubble diameter that more common air-floating apparatus generates is smaller, these bubbles can be stabilized the long period, substantially increase gas
Liquid mass transfer rate.
Another aspect of the invention is, provides a kind of production method of micro-nano bubble, the method includes following steps
It is rapid:
Step 1, successively piping connection gas-liquid mixing pump, pressure air-dissolving tank, ejector and water tank, composition can carry out fluid and follow
The micro-nano bubble generator of ring；
Specifically, the water inlet of pressure air-dissolving tank is directly connected with gas-liquid mixing pump, the water outlet of pressure air-dissolving tank with
Ejector is connected, and ejector injects fluid in water tank, and water tank connects gas-liquid mixing pump water inlet, constitutes a fluid circulation
System.
Step 2, liquid is added into water tank, starts each building blocks of function in micro-nano bubble generator, it is mixed to adjust gas-liquid
Air inflow in pump and ejector is closed, the micro-nano bubble met the requirements is generated.
Specifically, gas-liquid mixing pump sucks air, is sufficiently mixed the liquid being passed through by water tank and the air of sucking laggard
Entering pressure air-dissolving tank, forms high-pressure gas-liquid mixture, subsequently enter in ejector, the induction chamber of ejector can form negative pressure,
To making bubble release, the diffusion pipeline section after induction chamber there are pressurized effects can be by the bubble breaking released at more
Tiny bubble, that is, micro-nano bubble, is sprayed by outlet pipe.
Another aspect of the invention is, provides a kind of wastewater treatment equipment, and the waste water is organic wastewater, preferably contaminates
Expect waste water.
Preferably, the generating device structure having the same of the wastewater treatment equipment and above-mentioned micro-nano bubble, wherein
Liquid in wastewater treatment equipment is waste water.
Another aspect of the invention is, provides a kind of wastewater treatment method, preferably by above-mentioned wastewater treatment equipment into
Row processing, i.e., in terms of micro-nano bubble being applied to dye wastewater treatment.Specifically, each function structure in wastewater treatment equipment is connected
Part forms the wastewater treatment equipment that can carry out fluid circulation；It is passed through waste water into water tank, starts wastewater treatment equipment, carries out useless
Water process.Wastewater treatment equipment generates micro-nano bubble, micro-nano bubble collapse moment in waste water, and gas-liquid interface disappears, boundary
The chemical energy accumulated on face releases suddenly, and excitation generates free radicals, and is mainly hydroxyl radical free radical, reaction in these free radicals
The dissolved oxygen of water body is hypersaturated state in the process, and a greater variety of free radicals can be generated in conjunction with hydroxyl radical free radical, can
Non-selectivity ground degradation of contaminant, and secondary pollution will not be generated.
In a preferred embodiment, the waste water is waste water from dyestuff, preferably cationic dye wastewater, such as methylene
Base indigo plant waste water from dyestuff.
In micro-nano bubble application process, the degradation process of waste water can generate series of intermediate products, these intermediate productions
For object with assembling after micro-nano bubble floating, viscosity is larger, so that water surface reduction in surface tension, forms stable froth bed, this
A little foams can quantity to micro-nano bubble and stability have a huge impact, it is therefore necessary to take steps to eliminate the water surface
Foam reduces surface tension, avoids bubble coalescence from forming foam, improves the yield of free radical.
Reduce the waste water water surface on foam mode first is that defoaming agent is added into system.In the present invention, using defoaming agent
Tributyl phosphate, organic silicon defoamer, polyether antifoam agent, polyethers compound organosilicon defoaming agent are eliminated to be generated in wastewater treatment process
Foam, it is preferred to use polyethers compound organosilicon defoaming agent.
Organic silicon defoamer foam inhibition ability is strong, but poorly water-soluble, is easily accumulated on the water surface, causes secondary pollution；Polyethers
Class defoaming agent is water-soluble preferably, but foam inhibition limited time, dosage are relatively large.And tributyl phosphate defoaming agent toxicity is stronger,
It is not easy to operate.Thus, present invention preferably employs the defoaming agent of polyethers composite organic, bonding machine silicon defoaming agent and polyethers disappear
On the one hand the advantages of infusion, reduces defoaming agent dosage, another aspect defoaming agent can be slowly dissolved in water body, Bu Huizao
At secondary pollution or even greatly improve system COD.
Further, the present invention, which also passes through, changes different anti-foam agent concentration, pH value, reaction temperature etc., blister in reduction
Foam amount improves treatment effect.
The present inventor has found that pH value and the foaming degree of waste water from dyestuff are positively correlated after study.In acid condition, it contaminates
Expect molecule by a large amount of H+It surrounds, micro-nano bubble generates having electronic OH in degradation process, these free radicals are easy to attract just
Charge, to make system pH slowly rise, while mineralising dye molecule.Under alkaline condition, by a large amount of OH around dye molecule-
It surrounds, the OH- of free radical and negative electrical charge is mutually exclusive, and a large amount of bubbles is caused to dissolve out, and generates foam, and can not mineralising dyestuff point
Son.In the present invention, optimal reaction pH value is between 2~5, preferably 3~4.
The present inventors have additionally discovered that with the rising of reaction temperature, system percent of decolourization can also be improved, wherein 20~40 DEG C of decolorations
Rate is promoted most.Heating accelerates micro-nano bubble rising velocity and the speed that crumbles and fall, and produces more free radicals, is more advantageous to
The degradation of dye molecule, and temperature is increased to 40 DEG C or more, the dissolved oxygen of system is lower, may weaken the oxidative degradation of system
Effect, therefore percent of decolourization is smaller compared with 30 DEG C of promotion degree.Therefore, the present invention in, reaction temperature be 20~40 DEG C, preferably 20~
30℃。
In addition, present inventors have further discovered that, temperature is higher, and the dissolved oxygen decline in water causes bubble to be easy dissolution, because
This needs more defoaming agents to improve treatment effect, required to be positively correlated with anti-foam agent concentration and reaction temperature.Reaction temperature is situated between
When 20 DEG C~40 DEG C, the volumetric concentration of corresponding defoaming agent between 0.00045%~0.005%, preferably 0.00075%~
0.003%.
The present inventors have additionally discovered that suitable salt is added into waste water from dyestuff, reaction foamed phenomenon is suppressed, and then is improved
Water treatment effect.The salt selects solvable sulfate, solvable villaumite or solvable nitrate, preferably solvable sulfate such as sulfuric acid
Sodium.
Further, the concentration of the salt is between 0.5-5g/L, preferably 1-3g/L.The salt of concentration in above range, can
To reduce the pressure difference between bubble, thus keep bubble more stable and be not easy to gather the quantity for simultaneously dispersing to steep and also correspondingly increase, because
Free radical yield can be improved in this, promotes the mineralising of dye molecule, improves treatment effect.
Meanwhile as described above, micro-nano bubble is generated using ejector in the present invention, after ejector can will depressurize release
Bubble breaking reduces bubble diameter, can substantially alleviate the generation of foam；And extra foam can also pass through pressure air-dissolving
Tank body is discharged in the exhaust valve of tank.Therefore micro-nano bubble is relatively stable during degrading waste water, will not influence production free radical
Efficiency.
It is worth noting that, ejector, when gas-liquid mixture passes through induction chamber, liquid local pressure is lower than critical pressure,
Expand bubble in liquid rapidly, water-borne cavitation bubble flow through downstream diffusion pipeline section, pressure increases so that cavitation bubble is crumbled and fall,
Cavitation effect is generated, the high temperature and pressure that this effect generates can generate certain degradation effect to waste water.That is, this hair
In bright, waste water from dyestuff can not only degrade in water tank, can degrade simultaneously in ejector, improve the processing of waste water
Effect.
Embodiment
The preparation of the micro-nano bubble of embodiment 1
1, successively piping connection gas-liquid mixing pump, pressure air-dissolving tank, ejector and water tank, composition can carry out fluid circulation
It receives micro bubble generation device, pure water is injected into water tank；Wherein, the outlet pipeline of pressure air-dissolving tank is divided into two: one bye-passes
It is connected with ejector on branch 1, is connected with valve, pressure gauge and fluid flowmeter on another bye-pass, that is, branch 2；
2, start each building blocks of function in micro-nano bubble generator, adjust air inflow in gas-liquid mixing pump and ejector,
Generate the fluid containing micro-nano bubble.
Wherein, the ratio of ejector inspiratory capacity and 2 flow of branch is 1:250, sets the inspiratory capacity and branch of gas-liquid mixing pump
The ratio of 2 flow of road is 1:9.
Water sample by taking out certain volume in water tank fills vial, after 3~4h long-distance transportation, uses
Nanosight NS500 nano particle trace analysis instrument analyzes Air Bubble Size and particle diameter distribution, as a result as shown in Figure 3.
From the figure 3, it may be seen that the nano bubble in water sample between evenly dispersed a large amount of 100~300nm, this shows using this hair
Air inflow in the gas-liquid mixing pump and ejector of bright middle setting can actually play reduction gas by the cavitation effect of ejector
The effect of bulb diameter.
2 wastewater treatment of embodiment (pH=3)
1, successively piping connection gas-liquid mixing pump, pressure air-dissolving tank, ejector and water tank, composition can carry out fluid circulation
Wastewater treatment equipment injects 6mg/L aqueous solution of methylene blue into water tank, and adjusting aqueous solution pH is 3；Wherein, pressure air-dissolving tank
Outlet pipeline be divided on two: one bye-passes i.e. branch 1 and be connected with ejector, valve, pressure are connected on another bye-pass, that is, branch 2
Power table and fluid flowmeter；
2, start each building blocks of function in wastewater treatment equipment, adjust air inflow in gas-liquid mixing pump and ejector, at room temperature
Carry out wastewater treatment.Wherein, the ratio of ejector inspiratory capacity and 2 flow of branch is 1:250, sets the inspiratory capacity of gas-liquid mixing pump
Ratio with 2 flow of branch is 1:9.
3 wastewater treatment of embodiment (temperature+defoaming agent)
For methylene blue waste water treatment step with embodiment 2, difference, which is only that, further limits aqueous solution of methylene blue processing
Temperature is 20 DEG C, while anti-foam agent concentration is 0.00075%.
Wherein, used defoaming agent is that (Foshan city Xu Shi chemical science and technology is limited for polyethers compound organosilicon defoaming agent
Company DT-882D).
4 wastewater treatment of embodiment (temperature+defoaming agent)
Methylene blue waste water treatment step with embodiment 3, difference be only that limit aqueous solution of methylene blue treatment temperature as
30 DEG C, while anti-foam agent concentration is 0.00175%.
5 wastewater treatment of embodiment (temperature+defoaming agent)
Methylene blue waste water treatment step with embodiment 3, difference be only that limit aqueous solution of methylene blue treatment temperature as
40 DEG C, while anti-foam agent concentration is 0.003%.
6 wastewater treatment of embodiment (salt treatment)
For methylene blue waste water treatment step with embodiment 2, difference, which is only that, further limits aqueous solution of methylene blue processing
Temperature is 40 DEG C, while sodium sulphate is added, and sodium sulfate concentration is 2g/L in maintenance system.
7 wastewater treatment of embodiment (no salt treatment)
For methylene blue waste water treatment step with embodiment 2, difference, which is only that, further limits aqueous solution of methylene blue processing
Temperature is 40 DEG C, is added without sodium sulphate.
Comparative example
1 wastewater treatment of comparative example (pH=7)
For methylene blue waste water treatment step with embodiment 2, difference is only that the pH of aqueous solution of methylene blue is 7.
2 wastewater treatment of comparative example (pH=9)
For methylene blue waste water treatment step with embodiment 2, difference is only that the pH of aqueous solution of methylene blue is 9.
Experimental example
Experimental example 1
The treatment effect of 1~2 Methylene Blue aqueous solution of embodiment 2 and comparative example is compared, is measured in 1h respectively
Degradation efficiency of methylene blue under the conditions of pH=3,7 and 9, testing result are as shown in Figure 4.
From fig. 4, it can be seen that pH=3, under room temperature, 1h methylene indigo plant has apparent decolorizing effect, highest removal
Rate is 25.68%.Methylene blue is hardly degraded under the conditions of pH=7, pH=9.Reason may is that, in acid condition,
Methylene blue molecule is by a large amount of H+It surrounds, micro-nano bubble generates having electronic OH in degradation process, these free radicals are easy
Attract positive charge, to make system pH slowly rise, while mineralising methylene blue.Under alkaline condition, quilt around methylene blue
A large amount of OH-It surrounds, the OH of free radical and negative electrical charge-It is mutually exclusive, cause a large amount of bubbles to dissolve out, generates foam, therefore can not mineralising
Methylene blue.
Experimental example 2
The treatment effect of 3~5 Methylene Blue aqueous solution of embodiment is compared, is measured under different temperatures respectively
The methylene blue percent of decolourization at the interval 20min, while the 40 DEG C systems most to defoaming agent dosage have carried out TOC (total organic carbon
Content) measurement, it is as a result as shown in Figure 5 and Figure 6 respectively.
From fig. 5, it can be seen that with the rising of reaction temperature, system percent of decolourization can also be improved, wherein 40 DEG C of percent of decolourizations are most
Height, 20~30 DEG C of percent of decolourizations are promoted most.
From fig. 6, it can be seen that system TOC removal rate can achieve 60% or more under the conditions of 40 DEG C, it can be considered that disappearing
Infusion will not additionally improve the total organic content of whole system.
Experimental example 3
The treatment effect of 6~7 Methylene Blue aqueous solution of embodiment is compared, measures methylene blue decoloration respectively
Rate；COD (COD) test is carried out to embodiment 6 simultaneously, to be added after sulfate in system organic matter degradation situation into
It is capable to further determine that, as a result as shown in Figure 7 and Figure 8.
From figure 7 it can be seen that sulfate, which is added, can promote the decoloration of methylene blue, this addition for being primarily due to salt can
To reduce the pressure difference between bubble, thus keep bubble more stable and be not easy to gather the quantity for simultaneously dispersing to steep and also correspondingly increase, because
Free radical yield can be improved in this, promotes the mineralising of methylene blue.
And COD removal rate can reach 80% in Fig. 8, also turn out that the salting liquid of high concentration can effectively facilitate micro-nano gas
The degradation to organic matter is steeped, treatment effect is improved.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of generating device of micro-nano bubble, which is characterized in that described device includes the gas-liquid mixed of successively piping connection
(1), pressure air-dissolving tank (2), ejector (3) and water tank (4) are pumped,
Wherein, the lower end of the pressure air-dissolving tank (2) is water inlet, is connected directly with the water outlet of gas-liquid mixing pump (1), pressure
The upper end water outlet of dissolving (2) connects ejector (3)；The ejector (3) generates micro-nano bubble and will contain micro-nano
The fluid of bubble is passed through in water tank (4)；The water tank (4) and the water inlet of gas-liquid mixing pump (1) are connected directly, and form device
One circulatory system.
2. the apparatus according to claim 1, which is characterized in that be equipped with exhaust valve at the top of the pressure air-dissolving tank (2)
(21)；And/or
The outlet pipeline of the pressure air-dissolving tank (2), which is divided on two: one bye-passes i.e. branch 1, is connected with ejector (3), preferably props up
It is also connected with valve on road 1, valve, pressure gauge (5) and fluid flowmeter (6) are connected on another bye-pass, that is, branch 2.
3. the apparatus of claim 2, which is characterized in that adjust gas-liquid when generating micro-nano bubble using described device
Air inflow in mixing pump (1) and ejector (3)；
Preferably, the ratio of 2 flow of inspiratory capacity and branch of ejector (3) is set between 1:200~1:350, is preferably existed
Between 1:250~1:300；And/or
The ratio of 2 flow of inspiratory capacity and branch of gas-liquid mixing pump (1) is set between 1:8~1:12, preferably in 1:9~1:
Between 10.
4. a kind of wastewater treatment equipment, which is characterized in that
The generating device of micro-nano bubble structure having the same described in one of the wastewater treatment equipment and claims 1 to 3；
The waste water is organic wastewater, preferably waste water from dyestuff, more preferably cationic dye wastewater, as methylene blue dye is useless
Water.
5. a kind of wastewater treatment method, which is characterized in that handled by wastewater treatment equipment described in claim 4；
Preferably, it the described method comprises the following steps:
Step 1) connects each building blocks of function in wastewater treatment equipment, forms the wastewater treatment equipment that can carry out fluid circulation；
Step 2) is passed through waste water into water tank, starts wastewater treatment equipment, carries out wastewater treatment.
6. according to the method described in claim 5, it is characterized in that, further including adjusting gas-liquid mixing pump (1) and jet stream in step 2
Air inflow in device (3)；
Preferably, the ratio of 2 flow of inspiratory capacity and branch of ejector (3) is set between 1:200~1:350, is preferably existed
Between 1:250~1:300；And/or
The ratio of 2 flow of inspiratory capacity and branch of gas-liquid mixing pump (1) is set between 1:8~1:12, preferably in 1:9~1:
Between 10.
7. described to disappear according to the method described in claim 5, it is characterized in that, defoaming agent is added in treatment process into waste water
Infusion is selected from tributyl phosphate, organic silicon defoamer, polyether antifoam agent or polyethers compound organosilicon defoaming agent, and preferably polyethers is multiple
With organic silicon defoamer.
8. according to the method described in claim 5, it is characterized in that, the pH value for controlling waste water is 2~5, preferably when wastewater treatment
It is 3~4.
9. according to the method described in claim 5, it is characterized in that, when wastewater treatment, the treatment temperature for controlling waste water is 20~
40 DEG C, preferably 20~30 DEG C.
10. according to the method described in claim 5, it is characterized in that, treatment temperature is between 20 DEG C~40 DEG C when wastewater treatment
When, the volumetric concentration of corresponding defoaming agent is between 0.00045%~0.005%, preferably 0.00075%~0.003%.
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