CN106673104A - Preparation method and preparation device of coagulation type colloid bubbles - Google Patents

Preparation method and preparation device of coagulation type colloid bubbles Download PDF

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Publication number
CN106673104A
CN106673104A CN201710014055.1A CN201710014055A CN106673104A CN 106673104 A CN106673104 A CN 106673104A CN 201710014055 A CN201710014055 A CN 201710014055A CN 106673104 A CN106673104 A CN 106673104A
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bubble
coagulation type
liquid
type colloid
colloid
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CN201710014055.1A
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CN106673104B (en
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张明
卢晓丽
谢丽
周琪
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Tongji University
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Tongji University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron

Abstract

The invention provides a preparation method of coagulation type colloid bubbles. The preparation method comprises the following steps: mixing an ampholytic surfactant with a coagulant so as to obtain a bubble generation liquid; introducing air into the obtained bubble generation liquid, and stirring under a condition that the stirring velocity is 5000-8000rpm, thus obtaining the coagulation type colloid bubbles. The invention further provides a preparation device of the coagulation type colloid bubbles. According to the technical scheme of the invention, the bubble generation liquid has relatively high critical micelle concentration up to 122-307mg/L. The coagulation type colloid bubbles prepared by using the method provided by the invention are long in service life (liquid discharge time), i.e.,, 142-200 seconds, high in gas content, i.e., 53-55%, small in average diameter, i.e., 35-45[mu] m. By adopting the preparation method, the properties of the coagulation type colloid bubbles can be stable in the continuous gas floating separation process, and the sewage treatment effect can be improved.

Description

A kind of preparation method and preparation facilitiess of coagulation type colloid bubble
Technical field
The present invention relates to sewage air-flotation processing technology field, the preparation method of more particularly to a kind of coagulation type colloid bubble and Preparation facilitiess.
Background technology
Micron bubble has that specific surface area is big, the advantage that bubble density is high, is widely used in the air-flotation process process of sewage.It is right Micron bubble carries out surface modification, strengthen its targeting and catch the ability of pollutant and will become raising flotation waste water treatment efficiency, development gas The new direction of floating technique.The surface modification of micron bubble is typically carried out in the solution of flotation agent, flotation agent is generally table Face activating agent, on the one hand can reduce the surface tension of solution, be allowed to be easily formed bubble under certain disturbed conditions;It is another Aspect can further load other molecules or functional group in bubble surface, reach gas by Surfactant molecular modification The effect of bubble functionalization.
Colloid bubble is a kind of micron bubble with colloidal nature, and itself can be repaiied as feature bubble or bubble surface The carrier of decorations.The gas core of colloid bubble is coated by surfactant solution layer, and the surfactant solution layer is lived by double layer surface Property agent molecule formed, and bubble structure is stable to have third layer surfactant molecule to maintain in outside, and colloid bubble surface is charged Situation is determined by the surfactant for being used.In terms of the combination of bubble-pollutant is modified, strengthened in bubble surface to colloid bubble With very big potentiality:I () colloid bubble diameter is little, specific surface area big, fully can contact with pollutant;(ii) made by charge neutrality With the pollutant of specific adsorption oppositely charged;(iii) hydrophobic colloid bubble surface can strengthen the knot with hydrophobic contaminants Close, and be easy to be separated from water;(iv) Gas content of colloid bubble is higher, the floating upper separation that can be applied in air supporting;V () is stable Property be far above general foam, the pressure of about 27.3MPa can be born, can by pump by its from bubble generator transport to flotation tank And do not destroy the structure of bubble.
However, when colloid bubble is applied to purification of water quality and water remediation, only relying on surfactant molecule and target Colloid action power between pollutant (inhale for electrostatic by the colloid action power between ionic surfactant and target contaminant Draw, the colloid action power between nonionic surfactant and target contaminant is hydrophobic adsorbent), generally it is unable to reach very well Treatment effect;And the use of colloid bubble can be limited by critical micelle concentration of surfactant.
The content of the invention
It is an object of the invention to provide the preparation method and preparation facilitiess of a kind of coagulation type colloid bubble, using the present invention The life cycle length of the coagulation type colloid bubble that the method for offer is prepared, Gas content are high, average diameter is little, ensure that mixed Solidifying type colloid bubble retention propertiess in the continuous process for carrying out dissolved air flotation are stable, improve the treatment effect to sewage.
The invention provides a kind of preparation method of coagulation type colloid bubble, comprises the following steps:
(1) amphoteric surfactant is mixed with coagulant, obtains bubble and liquid occurs;
(2) bubble obtained to the step (1) occurs to be passed through air in liquid, is 5000~8000rpm in stir speed (S.S.) Under conditions of be stirred, obtain coagulation type colloid bubble.
Preferably, in the step (1), coagulant includes metal salt coagulant, inorganic polymer coagulant or organic polymer Thing flocculant.
Preferably, the metal salt coagulant includes FeCl3、AlCl3Or KAl (SO4)2·12H2O。
Preferably, the inorganic polymer coagulant includes aluminium polychlorid or poly-ferric chloride.
Preferably, the organic polvmer flocculant includes non-ionic polyacrylamide or Polyacrylamide.
Preferably, it is (30~67) that the flow and the bubble that air is passed through in the step (2) occurs the volume ratio of liquid mL/min:2000mL.
Preferably, in the step (2), the time of stirring is 60~90s.
The invention provides a kind of device for preparing coagulation type colloid bubble, including the gentle steep raising of bubble generation liquid bin Raw unit, the bubble holding unit (2) are provided with bubble and liquid inlet (11) and coagulation type colloid bubble liquid outlet occur (12) high speed agitator (5), is provided with the top of the bubble holding unit (2), bubble holding unit (2) bottom is provided with Air inlet (10), the air inlet (10) are communicated with gas flowmeter (9), and bubble holding unit (2) inwall is provided with gear Plate.
Preferably, when the quantity of the baffle plate is more than 1, the baffle plate equidistantly distributed.
Preferably, the bubble occurs agitator (6) is provided with the top of liquid bin (1), and the bubble occurs liquid storage There is liquid inlet (11) by water pump (7) and bubble and connect in device.
The invention provides a kind of preparation method of coagulation type colloid bubble, comprises the following steps:By amophoteric surface active Agent is mixed with coagulant, obtains bubble and liquid occurs;Occur to be passed through air in liquid to the bubble that obtains, stir speed (S.S.) be 5000~ It is stirred under conditions of 8000rpm, obtains coagulation type colloid bubble.The present invention is when prepared by micron bubble by its area load Coagulant composition, the coagulation type colloid bubble for preparing is applied in dissolved air flotation process, on the one hand can increase medicament The specific surface area contacted with target contaminant, is effectively targeted to remove target contaminant, is improving the same of contaminant removal efficiency When substantially reduce dosage;On the other hand independent dosing unit during follow-up air supporting is saved, processing cost is reduced.The present invention is carried For technical scheme in, there is liquid and have higher critical micelle concentration in bubble, up to 122~307mg/L.Carried using the present invention For the life cycle (drain time) of coagulation type colloid bubble for preparing of method it is long, be 142~200s;Gas content is high, For 53~55%;Average diameter is little, is 35~45 μm.This ensure that coagulation type colloid bubble is carrying out the continuous of dissolved air flotation During retention propertiess it is stable, improve the treatment effect to sewage.Test result indicate that, the coagulation type colloid that the present invention is provided Bubble is used for " bubble generation-dissolved air flotation " processing procedure, compared with " coagulation-dissolved air flotation " or " coagulation-precipitation ", equal Under dosage, wastewater treatment efficiency is significantly improved.
Meanwhile, the invention provides prepare the device of the coagulation type colloid bubble, including bubble occur liquid bin and Bubble holding unit, the bubble holding unit are provided with bubble and liquid inlet and coagulation type colloid bubble liquid outlet, institute occur State, the bubble holding unit bottom is provided with air inlet, the air inlet Mouth is communicated with gas flowmeter, and the bubble holding unit inwall is provided with baffle plate.What the present invention was provided prepares coagulation type colloid The device design of bubble is light and handy, without the need for individually arranging dispensing link again, arranges baffle plate in bubble holding unit inwall, while in gas Steep raising life unit bottom arranges air inlet, ensure that aeration is abundant and gas effciency is high in bubble generating process, can be 60 The strong coagulation type colloid bubble of uniform, favorable dispersibility, stability is obtained in~90s the times.
Description of the drawings
" bubble generation-dissolved air flotation " apparatus structure schematic diagram that Fig. 1 is provided for the present invention;
In figure 1 be bubble occur liquid bin, 2 be bubble holding unit, 3 be contact chamber, 4 be separate tank, 5 be high-speed stirring Mix device, 6 be agitator, 7 be water pump, 8 be water pump, 9 be gas flowmeter, 10 be air inlet, 11 be bubble occur liquid inlet, 12 is coagulation type colloid bubble liquid outlet, 13 is coagulation type colloid bubble inlet, 14 is water intake, 15 is air supporting clear liquid Outlet, 16 are scum trough slag notch.
Specific embodiment
The invention provides a kind of preparation method of coagulation type colloid bubble, comprises the following steps:
(1) amphoteric surfactant is mixed with coagulant, obtains bubble and liquid occurs;
(2) bubble obtained to the step (1) occurs to be passed through air in liquid, is 5000~8000rpm in stir speed (S.S.) Under conditions of be stirred, obtain coagulation type colloid bubble.
In the technical scheme that the present invention is provided, there is liquid with higher critical micelle concentration in bubble, reachable 122~ 307mg/L.The life cycle (drain time) of the coagulation type colloid bubble that the method provided using the present invention is prepared is long, is 142~200s;Gas content is high, is 53~55%;Coagulation type colloid bubble mean diameter is little, is 35~45 μm.This ensure that Coagulation type colloid bubble retention propertiess in the continuous process for carrying out dissolved air flotation are stable, improve the treatment effect to sewage.
Amphoteric surfactant is mixed by the present invention with coagulant, obtains bubble and liquid occurs.The present invention is for the both sexes The species of surfactant does not have special restriction, using the both sexes for preparing micron bubble well known to those skilled in the art Surfactant.Present invention preferably employs betaine type amphoteric surfac-tant;In an embodiment of the present invention, specifically adopt With dodecyldimethylammonium hydroxide inner salt as amphoteric surfactant.
In the present invention, the coagulant preferably includes metal salt coagulant, inorganic polymer coagulant or organic polymer Thing flocculant.In the present invention, the metal salt coagulant preferably includes FeCl3、AlCl3Or KAl (SO4)2·12H2O.At this In invention, the inorganic polymer coagulant preferably includes aluminium polychlorid or poly-ferric chloride.In the present invention, it is described organic Polymer flocculants preferably include non-ionic polyacrylamide or Polyacrylamide.In the present invention, select different The coagulant of species is mixed with amphoteric surfactant, can prepare lotus positive electricity, negative electricity or surface in electroneutral coagulation type Colloid bubble.
Species of the present invention preferably according to coagulant, selects the addition of the coagulant and amphoteric surfactant. In the present invention, when slaine coagulant is selected, the metal salt coagulant is preferably with the mass ratio of amphoteric surfactant (9.9~21.6):1.0, more preferably (12.4~15.4):1.0.In the present invention, when inorganic polymer coagulant is selected, The inorganic polymer coagulant is preferably (0.3~1.2) with the mass ratio of amphoteric surfactant:1.0, more preferably (0.6 ~0.9):1.0.In the present invention, when organic polvmer flocculant is selected, the organic polvmer flocculant and amphoteric surface The mass ratio of activating agent is preferably (0.2~1.8):1.0, more preferably (0.5~1.0):1.0.
In the present invention, the amphoteric surfactant is preferably carried out under agitation with the mixing of coagulant.This It is bright for it is described stirring there is no special restriction, using it is well known to those skilled in the art can be by the stirring of material mix homogeneously Technical scheme.In the present invention, the speed of the stirring is preferably 30~50rpm, more preferably 35~45rpm;Institute The time for stating stirring is preferably 4~7min.
After obtaining the bubble generation liquid, the present invention occurs to be passed through air in liquid to the bubble, in stir speed (S.S.) is It is stirred under conditions of 5000~8000rpm, obtains coagulation type colloid bubble.In the present invention, the stream for being passed through air Measure the volume ratio that liquid occurs with the bubble and be preferably (30~67) mL/min:2000mL, more preferably (40~55) mL/min: 2000mL.In the present invention, the stir speed (S.S.) is 5000~8000rpm, preferably 6000~7000rpm;The stirring Time is preferably 60~90s, more preferably 70~80s.
The invention provides a kind of device for preparing coagulation type colloid bubble, including the gentle steep raising of bubble generation liquid bin Raw unit, the bubble holding unit 2 are provided with bubble and liquid inlet 11 and coagulation type colloid bubble liquid outlet 12 occur, described Be provided with high speed agitator 5 at the top of bubble holding unit 2,2 bottom of the bubble holding unit is provided with air inlet 10, it is described enter QI KOU 10 is communicated with gas flowmeter 9, and 2 inwall of the bubble holding unit is provided with baffle plate.See Fig. 1.
The preparation facilitiess design of the coagulation type colloid bubble that the present invention is provided is light and handy, without the need for individually arranging dispensing link again, Baffle plate is set inside bubble holding unit, while air inlet is arranged in bubble holding unit bottom, ensure that bubble occurs During aeration it is abundant and gas effciency is high, uniform, favorable dispersibility, stability can be obtained within 60~90s times strong Coagulation type colloid bubble.
The device that the present invention is provided includes that bubble occurs liquid bin, and in the present invention, the bubble occurs liquid bin 1 It is preferred that being provided with agitator 6 at top, there is liquid bin 1 and preferably liquid inlet 11 occur with bubble by water pump 7 in the bubble Connection.See Fig. 1.The present invention does not have special restriction for the volume that the bubble occurs liquid bin 1, can be according to actual waste water Treating capacity is adjusted.In the present invention, the volume that the bubble occurs liquid bin 1 is preferably 5~6L.
The device that the present invention is provided includes bubble holding unit.The present invention does not have for the volume of the bubble holding unit 2 There is special restriction, can be adjusted according to actual waste water treating capacity.In the present invention, the volume of the bubble holding unit 2 Preferably 2000~2500mL.In the present invention, be there is into liquid in bubble bubble holding unit is pumped into from bubble generation liquid bin 1 2 flow is preferably 450~1700mL/min, most preferably more preferably 550~1350mL/min, 650~950mL/min. In the present invention, be passed through in the bubble holding unit 2 air flow be preferably 30~84mL/min, more preferably 37~ 67mL/min, most preferably 45~55mL/min.
The present invention is provided with baffle plate in 2 inwall of the bubble holding unit, when the quantity of the baffle plate is more than 1, described Baffle plate is preferably equidistantly distributed.In the present invention, the baffle plate is preferably shaped to rectangle.In the present invention, the gear One minor face of plate is preferably fixed to the bottom interior wall of the bubble holding unit 2, and an adjacent long side is preferably fixed to institute State the side inner walls of bubble holding unit 2.In the present invention, when the quantity of the baffle plate is more than 1, the baffle plate is preferably in institute The side inner walls equidistantly distributed of bubble holding unit 2 is stated, and with the axis of the bubble holding unit 2 as axis, two-by-two Between be mutually identical angle.In the present invention, the number of the baffle plate is preferably 3~4.In the present invention, specifically, when When the number of the baffle plate is 3, the baffle plate is mutually between any two with the axis of the bubble holding unit 2 as axis 120°;When the baffle plate number be 4 when, the baffle plate with the axis of the bubble holding unit 2 as axis, two-by-two it Between it is mutually in 90 °.In the present invention, in the bubble holding unit 2, under conditions of stir speed (S.S.) is 5000~8000rpm There is liquid to bubble to be stirred, baffle plate described in the bubbles strike of generation, be again introduced into bubble and liquid occurs, be conducive to gas core surface Continue cladding amphoteric surfactant molecular layer and modify, load coagulant composition;The baffle plate equidistantly distributed is conducive to keeping away Exempt from bubble generation liquid and vortex is produced in high-speed stirred, it is ensured that the even size distribution of the coagulation type colloid bubble for being generated.
The present invention does not have special restriction for the practical application device of the coagulation type colloid bubble, using this area skill Can be used in carrying out the device of dissolved air flotation process known to art personnel.In the present invention, carry out at the dissolved air flotation The device of reason is preferably included:Air-flotation process unit, the air-flotation process unit include contact chamber 3 and separate tank 4, the contact chamber The bottom of 3 side walls is provided with water intake 14, and the bottom of the contact chamber 3 is provided with coagulation type colloid bubble inlet 13, The bottom of 4 side wall of the separate tank is provided with air supporting clear liquid outlet 15, and the upper end of 4 side wall of the separate tank is provided with floating Slag chute slag notch 16;Wherein, the coagulation type colloid bubble liquid outlet 12 prepared in the device of the coagulation type colloid bubble passes through Water pump 8 is communicated with coagulation type colloid bubble inlet 13.See Fig. 1.
In actual applications, the coagulation type colloid bubble that the present invention is provided is preferably directly single to occur in the bubble The form of the coagulation type colloid bubble suspension obtained after stirring in unit carries out dissolved air flotation process to pollutant in target water body. In the present invention, the flow that waste water injects contact chamber 3 is preferably into 1083~4750mL/min, more preferably 2300~3500mL/ min.In the present invention, the coagulation type colloid bubble suspension is preferably (1~3) with the flow-rate ratio of waste water:5, concretely 1: 5、2:5 or 3:5.In the present invention, from the air supporting clear liquid outlet 15 discharge clear liquid flow be preferably the waste water with The 50%~70% of coagulation type colloid bubble suspension total flow, more preferably 55%~65%.In the present invention, from the scum silica frost The flow of the scum silica frost that groove slag notch 16 is discharged be preferably the waste water and coagulation type colloid bubble suspension total flow 30%~ 50%, more preferably 35%~45%;In actual production, the flow of the scum silica frost discharged from the scum trough slag notch 16 is concrete The stream of the clear liquid discharged is deducted from the air supporting clear liquid outlet 15 for the waste water and coagulation type colloid bubble suspension total flow Amount.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious So, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the reality in the present invention Example is applied, the every other embodiment obtained under the premise of creative work is not made by those of ordinary skill in the art all belongs to In the scope of protection of the invention.
Embodiment 1
(1) by 60mg/L (with Al2O3Meter) aluminium polychlorid (PACl) and 109mg/L dodecyldimethylammonium hydroxide inner salts mix Close, 5min is stirred under conditions of stir speed (S.S.) is 40rpm and obtains bubble generation liquid;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 33mL/min, is being stirred Speed is mixed 80s to be stirred under conditions of 6000rpm, obtains PACl- coagulation type colloid bubbles.
Aluminium polychlorid in step (1) is dispensed, common dodecyl dimethyl is prepared in the same manner sweet Dish alkali colloid bubble.
The product that step (2) stirring is prepared after terminating in embodiment 1 is actually PACl- coagulation type colloids bubble and hangs Liquid and common dodecyldimethylammonium hydroxide inner salt colloid bubble suspension, to the PACl- coagulations type colloid bubble suspension and commonly Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test:At ambient temperature, obtain freshly prepared Colloid bubble suspension to be measured import rapidly graduated cylinder, use electronics manual time-keeping, increase over time, the discharge opeing of colloid bubble until Graduated cylinder bottom liquid volume is caused to increase after rupture, when the colloid bubble into colloid bubble suspension to be measured is completely severed, as The discharge opeing of colloid bubble completely, stops timing.
The life cycle of colloid bubble is colloid bubble formation to discharge opeing completely time.Test result indicate that, common ten The life cycle of dialkyl dimethyl glycine betaine colloid bubble is about 128s, and the PACl- coagulation type colloid gas that the present invention is provided The life cycle of bubble is about 157s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, and life cycle improves about 23%.
The original bulk volume of colloid bubble suspension to be measured is calculated as V0, the final total volume of liquid obtained by when discharge opeing is complete is calculated as Vt, then the air content of colloid bubble be calculated by Formulas I:
Test result indicate that, the air content of common dodecyldimethylammonium hydroxide inner salt colloid bubble is 29%~43%, and The air content of the PACl- coagulation type colloid bubbles that the present invention is provided is 53%~55%, hence it is evident that higher than common dimethyl The air content of base glycine betaine colloid bubble.
The bubble diameter of colloid bubble is measured using the Mastersizer3000 laser particle analyzers of Malvern company of Britain, As a result show, a diameter of 50~60 μm of common dodecyldimethylammonium hydroxide inner salt colloid bubble, and the PACl- that the present invention is provided A diameter of 35~45 μm of coagulation type colloid bubble, hence it is evident that straight less than common dodecyldimethylammonium hydroxide inner salt colloid bubble Footpath.
To sum up experimental results, the life cycle length of the PACl- coagulation type colloid bubbles that the present invention is provided, air content High, diameter is little, illustrates that the PACl- coagulation type colloid bubbles of present invention offer have preferable stability.
Surface charge test is carried out to the PACl- coagulation type colloid bubbles that the present invention is provided, is as a result shown, the PACl- Coagulation type colloid bubble surface is positively charged.The PACl- coagulation type colloid bubble suspensions that embodiment 1 is prepared are directly used in " bubble generation-dissolved air flotation " continuous process processes the nanometer waste water (nano silicon of the electricity of bear containing surface, with SiO2Meter, 1400mg/L), after stable, when nanometer waste water is 5 with the flow-rate ratio of PACl- coagulation type colloid bubble suspensions:3rd, PACl Actual dosage is 22.5mg/L (with Al2O3Meter), hydraulic detention time (HRT) for 4.5min when, the removal of nano silicon Rate is up to 88%.The common dodecyldimethylammonium hydroxide inner salt colloid bubble suspension that embodiment 1 is prepared be used for " coagulation- Dissolved air flotation " continuous process processes identical nanometer waste water, specifically stirs pending nanometer waste water 30s in advance with 250rpm, throws Plus 1min is stirred with 200rpm again after coagulant PACl, 10min is stirred with 40rpm subsequently, common dodecyl two is finally passed through Methyl betaine colloid bubble suspension carries out floating upper separation 4.5min, wherein nanometer waste water and common dodecyl dimethyl Radix Betae The flow-rate ratio of alkali colloid bubble suspension is 5:3;To reach the sewage disposal effect suitable with " bubble generation-dissolved air flotation " method Really, then when adopting " coagulation-dissolved air flotation " method, the dosage of PACl is at least 38.1mg/L (with Al2O3Meter).Relatively understand, In the case that wastewater treatment efficiency is suitable, providing PACl- coagulation type colloid bubbles suspension by the present invention is used for " bubble generation-gas Floating separation " process, dosage are few, and process time is short.
It is continuous that the PACl- coagulation type colloid bubbles suspension that embodiment 1 is prepared is used for " bubble generation-dissolved air flotation " After process processes nanometer waste water, determined from air supporting clear liquid using ICP-AES (ICP-AES) Remaining Al content in the air supporting clear liquid that outlet is discharged, and remaining PACl amounts are converted into, then enter with the actual dosage of PACl Row compares, and as a result shows, the PACl more than 95% take part in dissolved air flotation process;It is organic to the dissolubility in the air supporting clear liquid Carbon (DOC) content is measured, and as a result shows, the DOC contents in the air supporting clear liquid do not increase.
Embodiment 2
(1) by 4.0mg/L (with Al2O3Meter) aluminium polychlorid (PACl) and 44mg/L dodecyldimethylammonium hydroxide inner salts mix Close, 6min is stirred under conditions of stir speed (S.S.) is 30rpm, obtain bubble and liquid occurs;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 30mL/min, is being stirred Speed is mixed 90s to be stirred under conditions of 5000rpm, obtains PACl- coagulation type colloid bubbles.
Aluminium polychlorid in step (1) is dispensed, common dodecyl dimethyl is prepared in the same manner sweet Dish alkali colloid bubble.
According to the method in embodiment 1, the PACl- coagulation type colloid bubble suspensions prepared by embodiment 2 with it is common Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test, as a result shows, common dimethyl The life cycle of base glycine betaine colloid bubble is about 108s, and the Life Cycle of the PACl- coagulation type colloid bubbles that the present invention is provided Phase is about 179s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, and life cycle improves about 33%, illustrates this The PACl- coagulation type colloid bubbles that invention is provided have preferable stability.
Surface charge test is carried out to the PACl- coagulation type colloid bubbles that the present invention is provided, is as a result shown, the PACl- Coagulation type colloid bubble surface is positively charged.The PACl- coagulation type colloid bubble suspensions that embodiment 2 is prepared are directly used in " bubble generation-dissolved air flotation " continuous process processes the nanometer waste water (nano silicon of the electricity of bear containing surface, with SiO2Meter, 97mg/L), after stable, under hydraulics same as Example 1 and operating condition, when the actual dosage of PACl is 1.5mg/L is (with Al2O3Meter) when, the clearance of nano silicon is up to 80%;Under identical hydraulics and treatment effect " coagulation-dissolved air flotation " process is compared, and the actual dosage of PACl reduces about 15%.
Embodiment 3
(1) by 1344mg/L (in terms of Fe (III)) iron chloride (FeCl3) and 109mg/L dodecyldimethylammonium hydroxide inner salts Mixing, stirs 4min under conditions of stir speed (S.S.) is 50rpm, obtains bubble and liquid occurs;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 35mL/min, is being stirred Speed is mixed 60s to be stirred under conditions of 8000rpm, obtains FeCl3- coagulation type colloid bubble.
Iron chloride in step (1) is dispensed, common dodecyldimethylammonium hydroxide inner salt is prepared in the same manner Colloid bubble.
According to the method in embodiment 1, the FeCl prepared to embodiment 33- coagulation type colloid bubble suspension with it is common Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test, as a result shows, common dimethyl The life cycle of base glycine betaine colloid bubble is about 132s, and the FeCl that the present invention is provided3The Life Cycle of-coagulation type colloid bubble Phase is about 190s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, and life cycle improves about 44%, illustrates this The FeCl that invention is provided3- coagulation type colloid bubble has preferable stability.
The FeCl provided by the present invention3- coagulation type colloid bubble carries out surface charge test, as a result shows, the FeCl3- Coagulation type colloid bubble surface is positively charged.The FeCl that embodiment 3 is prepared3- coagulation type colloid bubble suspension is directly used Alcohol waste water biochemical treatment water outlet is processed in " bubble generation-dissolved air flotation " continuous process, and (colourity is about 960 black increasings, dissolubility The content of organic carbon DOC is about 197mg/L), investigate decolourize, except Organic substance effect.After stable, when pH value of waste water is 7.0, Waste water and FeCl3- coagulation type colloid bubble suspension flow-rate ratio is 3:1, FeCl3Actual dosage be 336mg/L (with Fe (III) Meter), hydraulic detention time (HRT) for 4min when, chroma removal rate is up to 93%, DOC clearances up to 70%.Using " coagulation- Precipitation " process processes identical alcohol waste water biochemical treatment water outlet, specifically stirs pending waste water 30s in advance with 250rpm, throws Plus coagulant FeCl31min is stirred with 200rpm again afterwards, 10min is stirred with 40rpm subsequently, supernatant survey after precipitation 20min, is taken Determine DOC and colourity.In coagulant FeCl3Dosage identical in the case of, the percent of decolourization and DOC of " coagulation-precipitation " process go Except rate is only 68% and 48%;To reach the treatment effect suitable with " bubble generation-dissolved air flotation " method, " coagulation-precipitation " During FeCl3Dosage be at least 840mg/L (in terms of Fe (III)).Relatively understand, in the suitable feelings of wastewater treatment efficiency Under condition, FeCl is provided by the present invention3- coagulation type colloid bubble suspension is used for " bubble generation-dissolved air flotation " process, dosage Few, process time is short.
Embodiment 4
(1) by 1680mg/L (in terms of Fe (III)) iron chloride (FeCl3) and 109mg/L dodecyldimethylammonium hydroxide inner salts Mixing, stirs 4min under conditions of stir speed (S.S.) is 50rpm, obtains bubble and liquid occurs;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 35mL/min, is being stirred Speed is mixed 60s to be stirred under conditions of 8000rpm, obtains FeCl3- coagulation type colloid bubble.
Iron chloride in step (1) is dispensed, common dodecyldimethylammonium hydroxide inner salt is prepared in the same manner Colloid bubble.
According to the method in embodiment 1, the FeCl prepared to embodiment 43- coagulation type colloid bubble suspension with it is common Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test, as a result shows, common dimethyl The life cycle of base glycine betaine colloid bubble is about 125s, and the FeCl that the present invention is provided3The Life Cycle of-coagulation type colloid bubble Phase is about 176s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, and life cycle improves about 41%, illustrates this The FeCl that invention is provided3- coagulation type colloid bubble has preferable stability.
The FeCl provided by the present invention3- coagulation type colloid bubble carries out surface charge test, as a result shows, the FeCl3- Coagulation type colloid bubble surface is positively charged.The FeCl that embodiment 4 is prepared3- coagulation type colloid bubble suspension is directly used Waste water in " bubble generation-dissolved air flotation " continuous process Processing Example 3.After stable, same as Example 3 Under hydraulics and operating condition, FeCl3Actual dosage be 420mg/L (in terms of Fe (III)) when, chroma removal rate is reachable 85%, DOC clearance is up to 78%;Under equal dosage, the percent of decolourization and DOC clearances of " coagulation-precipitation " process are only 75% and 56%.
Embodiment 5
(1) by 1344mg/L (in terms of Fe (III)) iron chloride (FeCl3) and 109mg/L dodecyldimethylammonium hydroxide inner salts Mixing, stirs 4min under conditions of stir speed (S.S.) is 50rpm, obtains bubble and liquid occurs;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 35mL/min, is being stirred Speed is mixed 60s to be stirred under conditions of 8000rpm, obtains FeCl3- coagulation type colloid bubble.
Iron chloride in step (1) is dispensed, common dodecyldimethylammonium hydroxide inner salt is prepared in the same manner Colloid bubble.
According to the method in embodiment 1, the FeCl prepared to embodiment 53- coagulation type colloid bubble suspension with it is common Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test, as a result shows, common dimethyl The life cycle of base glycine betaine colloid bubble is 132s, and the FeCl that the present invention is provided3The life cycle of-coagulation type colloid bubble For 190s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, life cycle improve about 44%, illustrate the present invention The FeCl of offer3- coagulation type colloid bubble has preferable stability.
The FeCl provided by the present invention3- coagulation type colloid bubble carries out surface charge test, as a result shows, the FeCl3- Coagulation type colloid bubble surface is positively charged.The FeCl that embodiment 5 is prepared3- coagulation type colloid bubble suspension is directly used Waste water in " bubble generation-dissolved air flotation " continuous process Processing Example 3.After stable, when pH value of waste water is 9.0, Under hydraulics same as Example 3 and operating condition, FeCl3Actual dosage be 336mg/L (in terms of Fe (III)) When, chroma removal rate is up to 88%, DOC clearances up to 75%;Under equal dosage, the percent of decolourization of " coagulation-precipitation " process It is only 70% and 57% with DOC clearances.
Embodiment 6
(1) by 1344mg/L (in terms of Fe (III)) iron chloride (FeCl3) and 109mg/L dodecyldimethylammonium hydroxide inner salts Mixing, stirs 4min under conditions of stir speed (S.S.) is 50rpm, obtains bubble and liquid occurs;
(2) bubble obtained to step (1) occurs to be passed through air in liquid, and the flow for being passed through air is 35mL/min, is being stirred Speed is mixed 60s to be stirred under conditions of 8000rpm, obtains FeCl3- coagulation type colloid bubble.
Iron chloride in step (1) is dispensed, common dodecyldimethylammonium hydroxide inner salt is prepared in the same manner Colloid bubble.
According to the method in embodiment 1, the FeCl prepared to embodiment 63- coagulation type colloid bubble suspension with it is common Dodecyldimethylammonium hydroxide inner salt colloid bubble suspension carries out discharge opeing dynamic test, as a result shows, common dimethyl The life cycle of base glycine betaine colloid bubble is 132s, and the FeCl that the present invention is provided3The life cycle of-coagulation type colloid bubble For 190s, and common dodecyldimethylammonium hydroxide inner salt colloid bubble phase ratio, life cycle improve about 44%, illustrate the present invention The FeCl of offer3- coagulation type colloid bubble has preferable stability.
The FeCl provided by the present invention3- coagulation type colloid bubble carries out surface charge test, as a result shows, the FeCl3- Coagulation type colloid bubble surface is positively charged.The FeCl that embodiment 6 is prepared3- coagulation type colloid bubble suspension is directly used Waste water in " bubble generation-dissolved air flotation " continuous process Processing Example 3.After stable, when pH value of waste water is 5.0, Under hydraulics same as Example 3 and operating condition, FeCl3Actual dosage be 336mg/L (in terms of Fe (III)) When, chroma removal rate is up to 72%, DOC clearances up to 61%;Under equal dosage, the percent of decolourization of " coagulation-precipitation " process It is only 65% and 49% with DOC clearances.
Embodiment 7
Critical micelle concentration of the amphoteric surfactant with the mixed solution and amphoteric surfactant of coagulant is carried out Test, wherein, the amphoteric surfactant by taking dodecyldimethylammonium hydroxide inner salt (BS-12) as an example, the coagulant with PACl、FeCl3As a example by non-ionic polyacrylamide;Solution to be measured is specially:
Solution I:BS-12 aqueous solutions, wherein, the mass concentration scope of BS-12 is 9.8~2508.2mg/L;
Solution II:The mixed aqueous solution of BS-12 and PACl, wherein, the mass concentration scope of BS-12 is 9.8~ The mass concentration of 2508.2mg/L, PACl is 1.3mg/L (with Al2O3Meter);
Solution III:BS-12 and FeCl3Mixed aqueous solution, wherein, the mass concentration scope of BS-12 is 9.8~ 2508.2mg/L, FeCl3Mass concentration be 224mg/L (in terms of Fe (III));
Solution IV:The mixed aqueous solution of BS-12 and non-ionic polyacrylamide, wherein, the mass concentration scope of BS-12 For 9.8~2508.2mg/L, the mass concentration of non-ionic polyacrylamide is 3mg/L.
The present invention at ambient temperature, is entered to the critical micelle concentration of the solution I~solution IV using surface tension method Row test, the mass concentration of surface tension BS-12 corresponding when reaching minimum are critical micelle concentration, and experimental result is shown in Table 1, in table 1, the critical micelle concentration (mg/L) and corresponding molar concentration (mmol/L) are with the mass concentration of BS-12 Meter.As shown in Table 1, the critical micelle concentration of the mixed solution obtained after mixed BS-12 with coagulant can be significantly higher than described The critical micelle concentration of BS-12, this ensure that the present invention offer bubble occur liquid can concentration scope (with BS-12 Molar concentration meter) it is wider, and further expand the use range of the coagulation type colloid bubble that the present invention is provided.
The mixed solution and the critical micelle concentration of BS-12 of 1 BS-12 of table and coagulant
Solution to be measured Critical micelle concentration (mg/L) Molar concentration (mmol/L)
Solution I 90.9 0.29
Solution II 235.1 0.75
Solution III 307.2 0.98
Solution IV 122.3 0.39
The coagulation type glue that the method provided using the present invention is prepared is can be seen that by above example and result of the test The life cycle (drain time) of matter bubble is long, is 142~200s;Gas content is high, is 53~55%;Coagulation type colloid bubble is put down Diameter is little, is 35~45 μm;Can be in wider array of pH value range (such as FeCl3The applicable pH value model of-coagulation type colloid bubble Enclose for 5~9) there is preferable removal effect to target contaminant.This ensure that coagulation type colloid bubble is carrying out dissolved air flotation Continuous process in retention propertiess it is stable, improve the treatment effect to sewage.The coagulation type colloid bubble that the present invention is provided should In for actual sewage process, compared with other air flotation technologies, the specific surface area that medicament is contacted with target contaminant can be increased, It is effectively targeted to remove target contaminant, reduces hydraulic detention time, substantially reduces while contaminant removal efficiency is improved Dosage;Without the need for individually arranging dispensing link again, handling process floor space and cost are saved;Treatment effeciency is significantly improved, is imitated Fruit strengthens, dosage is greatly decreased, and saves dispensing cost, it is to avoid introduce water body organic contamination because overdose is added, useless In water treatment field, application is strong.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of coagulation type colloid bubble, comprises the following steps:
(1) amphoteric surfactant is mixed with coagulant, obtains bubble and liquid occurs;
(2) bubble obtained to the step (1) occurs to be passed through air in liquid, in the bar that stir speed (S.S.) is 5000~8000rpm It is stirred under part, obtains coagulation type colloid bubble.
2. preparation method according to claim 1, it is characterised in that coagulant includes that slaine is mixed in the step (1) Solidifying agent, inorganic polymer coagulant or organic polvmer flocculant.
3. preparation method according to claim 2, it is characterised in that the metal salt coagulant includes FeCl3、AlCl3Or KAl(SO4)2·12H2O。
4. preparation method according to claim 2, it is characterised in that the inorganic polymer coagulant, including polymerization chlorine Change aluminum or poly-ferric chloride.
5. preparation method according to claim 2, it is characterised in that the organic polvmer flocculant includes nonionic Polyacrylamide or Polyacrylamide.
6. preparation method according to claim 1, it is characterised in that flow and the institute of air are passed through in the step (2) The volume ratio for stating bubble generation liquid is (30~67) mL/min:2000mL.
7. the preparation method according to claim 1 or 6, it is characterised in that in the step (2) time of stirring be 60~ 90s。
8. liquid bin and bubble holding unit, its feature there is in a kind of device for preparing coagulation type colloid bubble, including bubble It is that the bubble holding unit (2) is provided with bubble and liquid inlet (11) and coagulation type colloid bubble liquid outlet (12) occur, High speed agitator (5) is provided with the top of the bubble holding unit (2), bubble holding unit (2) bottom is provided with air inlet Mouth (10), the air inlet (10) are communicated with gas flowmeter (9), and bubble holding unit (2) inwall is provided with baffle plate.
9. device according to claim 8, it is characterised in that when the quantity of the baffle plate is more than 1, between described baffle plate etc. Away from distribution.
10. device according to claim 8 or claim 9, it is characterised in that the bubble occurs to arrange at the top of liquid bin (1) There is agitator (6), the bubble is occurred liquid bin and connected by water pump (7) and bubble generation liquid inlet (11).
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