CN106673104B - Preparation method and preparation device of coagulated colloid bubbles - Google Patents

Preparation method and preparation device of coagulated colloid bubbles Download PDF

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CN106673104B
CN106673104B CN201710014055.1A CN201710014055A CN106673104B CN 106673104 B CN106673104 B CN 106673104B CN 201710014055 A CN201710014055 A CN 201710014055A CN 106673104 B CN106673104 B CN 106673104B
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bubble
bubble generation
bubbles
colloid
coagulant
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CN106673104A (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 coagulated colloid bubbles, which comprises the following steps: mixing an amphoteric surfactant and a coagulant to obtain a bubble generation liquid; and introducing air into the obtained bubble generation liquid, and stirring at the stirring speed of 5000-8000 rpm to obtain the coagulated colloidal bubbles. Meanwhile, the invention provides a device for preparing the coagulated colloid bubble. In the technical scheme provided by the invention, the bubble generating liquid has higher critical micelle concentration which can reach 122-307 mg/L. The life cycle (liquid drainage time) of the coagulated colloidal bubbles prepared by the method provided by the invention is long and is 142-200 s; the gas content is high and is 53-55%; the average diameter of the coagulated colloid bubbles is small and is 35-45 mu m. The method can ensure that the coagulation type colloidal bubbles keep stable in the continuous process of air floatation separation, and improve the treatment effect on sewage.

Description

Preparation method and preparation device of coagulated colloid bubbles
Technical Field
The invention relates to the technical field of sewage air floatation treatment, in particular to a preparation method and a preparation device of coagulated colloid bubbles.
Background
The micron bubble has the advantages of large specific surface area and high bubble density, and is widely used for the air floatation treatment process of sewage. The surface modification of the micro-bubbles and the enhancement of the capability of the micro-bubbles for capturing pollutants in a targeted manner become a new direction for improving the air-flotation water purification efficiency and developing the air-flotation process. The surface modification of the micro-bubbles is usually carried out in a solution of a flotation agent, and the flotation agent is generally a surfactant, so that on one hand, the surface tension of the solution can be reduced, and the solution is easy to form bubbles under certain disturbance conditions; on the other hand, the surface of the air bubbles can be further loaded with other molecules or functional groups by modifying the molecules of the surfactant, so that the air bubbles are functionalized.
The colloid bubble is a micron bubble with colloid property, and can be used as a carrier for functional bubbles or surface modification of bubbles. The gas core of the colloid bubble is coated by a surfactant solution layer, the surfactant solution layer is formed by double layers of surfactant molecules, a third layer of surfactant molecules is arranged outside the surfactant solution layer to maintain the stability of the bubble structure, and the surface charge condition of the colloid bubble is determined by the used surfactant. The colloid bubble has great potential in the aspects of bubble surface modification and bubble-pollutant combination strengthening: (i) the colloid bubbles have small diameter and large specific surface area and can be fully contacted with pollutants; (ii) specifically adsorbing oppositely charged contaminants by electrical neutralization; (iii) the hydrophobic colloid bubble surface can strengthen the combination with hydrophobic pollutants and is easy to separate from water; (iv) the colloid bubbles have high gas content and can be applied to floatation separation in air floatation; (v) the stability is far higher than that of common foam, the foam can bear the pressure of about 27.3MPa, and the foam can be transported to the air floatation tank from the bubble generator through a pump without damaging the structure of the bubbles.
However, when the colloidal bubbles are applied to water purification and water body restoration, a good treatment effect cannot be achieved only by the colloidal acting force between the surfactant molecules and the target pollutants (the colloidal acting force between the ionic surfactant and the target pollutants is electrostatic attraction, and the colloidal acting force between the nonionic surfactant and the target pollutants is hydrophobic adsorption); and the use of colloidal bubbles is limited by the critical micelle concentration of the surfactant.
Disclosure of Invention
The invention aims to provide a preparation method and a preparation device of coagulated colloidal bubbles, and the coagulated colloidal bubbles prepared by the method have long life cycle, high gas content and small average diameter, can ensure that the coagulated colloidal bubbles keep stable in the continuous process of air floatation separation, and improve the treatment effect on sewage.
The invention provides a preparation method of coagulated colloid bubbles, which comprises the following steps:
(1) mixing an amphoteric surfactant and a coagulant to obtain a bubble generation liquid;
(2) and (2) introducing air into the bubble generation liquid obtained in the step (1), and stirring at the stirring speed of 5000-8000 rpm to obtain the coagulated colloidal bubbles.
Preferably, the coagulant in the step (1) comprises a metal salt coagulant, an inorganic polymer coagulant or an organic polymer flocculant.
Preferably, the metal salt coagulant comprises FeCl3、AlCl3Or KAl (SO)4)2·12H2O。
Preferably, the inorganic polymeric coagulant comprises polyaluminium chloride or polyferric chloride.
Preferably, the organic polymer flocculant comprises a non-ionic polyacrylamide or an ionic polyacrylamide.
Preferably, the volume ratio of the flow rate of the air introduced in the step (2) to the bubble generation liquid is (30-67) mL/min: 2000 mL.
Preferably, the stirring time in the step (2) is 60-90 s.
The invention provides a device for preparing coagulation type colloidal bubbles, which comprises a bubble generation liquid storage and a bubble generation unit, wherein the bubble generation unit (2) is provided with a bubble generation liquid inlet (11) and a coagulation type colloidal bubble outlet (12), the top of the bubble generation unit (2) is provided with a high-speed stirrer (5), the bottom of the bubble generation unit (2) is provided with an air inlet (10), the air inlet (10) is communicated with a gas flowmeter (9), and the inner wall of the bubble generation unit (2) is provided with a baffle.
Preferably, when the number of the baffles is more than 1, the baffles are distributed at equal intervals.
Preferably, a stirrer (6) is arranged at the top of the bubble generation liquid storage (1), and the bubble generation liquid storage is communicated with a bubble generation liquid inlet (11) through a water pump (7).
The invention provides a preparation method of coagulated colloid bubbles, which comprises the following steps: mixing an amphoteric surfactant and a coagulant to obtain a bubble generation liquid; and introducing air into the obtained bubble generation liquid, and stirring at the stirring speed of 5000-8000 rpm to obtain the coagulated colloidal bubbles. In the invention, coagulant components are loaded on the surface of the micro-bubbles during preparation, and the prepared coagulated colloidal bubbles are applied to air floatation separation treatment, so that on one hand, the specific surface area of a medicament in contact with a target pollutant can be increased, the target pollutant can be effectively removed in a targeted manner, the pollutant removal efficiency is improved, and the dosage is obviously reduced; on the other hand, a separate medicine adding unit in the subsequent air floatation process is omitted, and the treatment cost is reduced. In the technical scheme provided by the invention, the bubble generating liquid has higher critical micelle concentration which can reach 122-307 mg/L. The life cycle (liquid drainage time) of the coagulated colloidal bubbles prepared by the method provided by the invention is long and is 142-200 s; the gas content is high and is 53-55%; the average diameter is small and is 35-45 μm. The method can ensure that the coagulation type colloidal bubbles keep stable in the continuous process of air floatation separation, and improve the treatment effect on sewage. Experimental results show that when the coagulation type colloid bubbles provided by the invention are used in the treatment process of bubble generation-air flotation separation, compared with coagulation-air flotation separation or coagulation-precipitation, the sewage treatment effect is obviously improved under the same dosage.
Meanwhile, the invention provides a device for preparing the coagulation type colloid bubble, which comprises a bubble generation liquid storage and a bubble generation unit, wherein the bubble generation unit is provided with a bubble generation liquid inlet and a coagulation type colloid bubble outlet, the top of the bubble generation unit is provided with a high-speed stirrer, the bottom of the bubble generation unit is provided with an air inlet, the air inlet is communicated with a gas flowmeter, and the inner wall of the bubble generation unit is provided with a baffle plate. The device for preparing the coagulation type colloid bubbles is light and handy in design, a chemical feeding link does not need to be independently arranged, the baffle is arranged on the inner wall of the bubble generation unit, and the air inlet is arranged at the bottom of the bubble generation unit, so that sufficient aeration and high gas utilization rate can be ensured in the bubble generation process, and the coagulation type colloid bubbles with uniformity, good dispersibility and strong stability can be prepared within 60-90 s.
Drawings
FIG. 1 is a schematic structural view of a "bubble generation-air flotation separation" apparatus according to the present invention;
in the figure, 1 is a bubble generation liquid storage, 2 is a bubble generation unit, 3 is a contact tank, 4 is a separation tank, 5 is a high-speed stirrer, 6 is a stirrer, 7 is a water pump, 8 is a water pump, 9 is a gas flow meter, 10 is an air inlet, 11 is a bubble generation liquid inlet, 12 is a coagulation type colloid bubble liquid outlet, 13 is a coagulation type colloid bubble liquid inlet, 14 is a wastewater inlet, 15 is an air flotation clear liquid outlet, and 16 is a scum groove slag outlet.
Detailed Description
The invention provides a preparation method of coagulated colloid bubbles, which comprises the following steps:
(1) mixing an amphoteric surfactant and a coagulant to obtain a bubble generation liquid;
(2) and (2) introducing air into the bubble generation liquid obtained in the step (1), and stirring at the stirring speed of 5000-8000 rpm to obtain the coagulated colloidal bubbles.
In the technical scheme provided by the invention, the bubble generating liquid has higher critical micelle concentration which can reach 122-307 mg/L. The life cycle (liquid drainage time) of the coagulated colloidal bubbles prepared by the method provided by the invention is long and is 142-200 s; the gas content is high and is 53-55%; the average diameter of the coagulated colloid bubbles is small and is 35-45 mu m. The method can ensure that the coagulation type colloidal bubbles keep stable in the continuous process of air floatation separation, and improve the treatment effect on sewage.
The invention mixes the amphoteric surfactant and the coagulant to obtain the bubble generation liquid. The present invention is not particularly limited in the kind of the amphoteric surfactant, and an amphoteric surfactant for producing microbubbles known to those skilled in the art may be used. The invention preferably adopts betaine type amphoteric surfactant; in the examples of the present invention, dodecyl dimethyl betaine is specifically used as the amphoteric surfactant.
In the present invention, the coagulant preferably comprises a metal salt coagulant, an inorganic polymer coagulant or an organic polymer flocculant. In the present invention, the metal salt coagulant preferably comprises FeCl3、AlCl3Or KAl (SO)4)2·12H2And O. In the present invention, the inorganic polymer coagulant preferably comprises polyaluminum chloride or polyferric chloride. In the present invention, the organic polymer flocculant preferably comprises a nonionic polyacrylamide or an ionic polyacrylamide. In the invention, different coagulants are selected and mixed with the amphoteric surfactant to prepare the coagulation type colloid bubble with positive charge, negative charge or neutral surface.
In the present invention, the amounts of the coagulant and the amphoteric surfactant to be added are preferably selected according to the type of the coagulant. In the invention, when the metal salt coagulant is selected, the mass ratio of the metal salt coagulant to the amphoteric surfactant is preferably (9.9-21.6): 1.0, more preferably (12.4 to 15.4): 1.0. in the invention, when the inorganic polymer coagulant is selected, the mass ratio of the inorganic polymer coagulant to the amphoteric surfactant is preferably (0.3-1.2): 1.0, more preferably (0.6 to 0.9): 1.0. in the invention, when the organic polymer flocculant is selected, the mass ratio of the organic polymer flocculant to the amphoteric surfactant is preferably (0.2-1.8): 1.0, more preferably (0.5 to 1.0): 1.0.
in the present invention, the mixing of the amphoteric surfactant and the coagulant is preferably performed under stirring conditions. The stirring is not particularly limited, and the technical scheme of uniformly mixing materials, which is well known to those skilled in the art, can be adopted. In the invention, the stirring speed is preferably 30-50 rpm, and more preferably 35-45 rpm; the stirring time is preferably 4-7 min.
After the bubble generation liquid is obtained, the air is introduced into the bubble generation liquid, and the mixture is stirred at the stirring speed of 5000-8000 rpm to obtain the coagulation type colloidal bubbles. In the invention, the volume ratio of the flow rate of the introduced air to the bubble generation liquid is preferably (30-67) mL/min: 2000mL, more preferably (40 to 55) mL/min: 2000 mL. In the invention, the stirring speed is 5000-8000 rpm, preferably 6000-7000 rpm; the stirring time is preferably 60-90 s, and more preferably 70-80 s.
The invention provides a device for preparing coagulation type colloidal bubbles, which comprises a bubble generation liquid storage and a bubble generation unit, wherein the bubble generation unit 2 is provided with a bubble generation liquid inlet 11 and a coagulation type colloidal bubble liquid outlet 12, the top of the bubble generation unit 2 is provided with a high-speed stirrer 5, the bottom of the bubble generation unit 2 is provided with an air inlet 10, the air inlet 10 is communicated with a gas flowmeter 9, and the inner wall of the bubble generation unit 2 is provided with a baffle plate. See fig. 1.
The preparation device for the coagulated colloid bubbles provided by the invention is light in design, a chemical feeding link is not required to be independently arranged, the baffle is arranged in the bubble generation unit, and the air inlet is arranged at the bottom of the bubble generation unit, so that sufficient aeration and high gas utilization rate can be ensured in the bubble generation process, and the coagulated colloid bubbles with uniformity, good dispersibility and strong stability can be prepared within 60-90 s.
The device provided by the invention comprises a bubble generation liquid storage device, wherein the bubble generation liquid storage device 1 is preferably provided with a stirrer 6 at the top, and the bubble generation liquid storage device 1 is preferably communicated with a bubble generation liquid inlet 11 through a water pump 7. See fig. 1. The volume of the bubble generation liquid reservoir 1 is not particularly limited, and can be adjusted according to the actual wastewater treatment amount. In the invention, the volume of the bubble generation liquid storage 1 is preferably 5-6L.
The device provided by the invention comprises a bubble generation unit. The volume of the bubble generation unit 2 is not particularly limited, and can be adjusted according to the actual wastewater treatment amount. In the present invention, the volume of the bubble generation unit 2 is preferably 2000 to 2500 mL. In the present invention, the flow rate of the bubble generation liquid pumped from the bubble generation liquid reservoir 1 to the bubble generation unit 2 is preferably 450 to 1700mL/min, more preferably 550 to 1350mL/min, and most preferably 650 to 950 mL/min. In the present invention, the flow rate of the air introduced into the bubble generation unit 2 is preferably 30 to 84mL/min, more preferably 37 to 67mL/min, and most preferably 45 to 55 mL/min.
The inner wall of the bubble generation unit 2 is provided with baffles, and when the number of the baffles is more than 1, the baffles are preferably distributed at equal intervals. In the present invention, the shape of the baffle is preferably rectangular. In the present invention, one short side of the baffle is preferably fixed to the bottom inner wall of the bubble generation unit 2, and the adjacent one long side is preferably fixed to the side inner wall of the bubble generation unit 2. In the present invention, when the number of the baffles is greater than 1, the baffles are preferably distributed on the inner wall of the side surface of the bubble generation unit 2 at equal intervals, and the central axis of the bubble generation unit 2 is used as the central axis, and the baffles form the same angle with each other. In the invention, the number of the baffles is preferably 3-4. In the invention, specifically, when the number of the baffles is 3, the baffles take the central axis of the bubble generation unit 2 as a central axis, and the angles between every two baffles are 120 degrees; when the number of the baffles is 4, the baffles take the central axis of the bubble generating unit 2 as a central axis, and the angle between every two baffles is 90 degrees. In the invention, in the bubble generation unit 2, the bubble generation liquid is stirred under the condition that the stirring speed is 5000-8000 rpm, generated bubbles impact the baffle and enter the bubble generation liquid again, which is beneficial to continuously coating the gas core surface with an amphoteric surfactant molecular layer, modifying and loading coagulant components; the baffle plates are distributed at equal intervals, so that the bubble generation liquid is prevented from generating vortex during high-speed stirring, and the generated coagulation type colloidal bubbles are ensured to be uniformly distributed in size.
The actual application device of the coagulated colloidal bubbles is not particularly limited, and devices for air-flotation separation treatment known to those skilled in the art may be used. In the present invention, the apparatus for performing the air flotation separation treatment preferably includes: the air flotation treatment unit comprises a contact tank 3 and a separation tank 4, a wastewater inlet 14 is formed in the lower end of the side wall of the contact tank 3, a coagulation type colloid bubble inlet 13 is formed in the bottom of the contact tank 3, an air flotation clear liquid outlet 15 is formed in the lower end of the side wall of the separation tank 4, and a scum groove slag outlet 16 is formed in the upper end of the side wall of the separation tank 4; wherein, a coagulation type colloid bubble liquid outlet 12 in the device for preparing the coagulation type colloid bubbles is communicated with a coagulation type colloid bubble liquid inlet 13 through a water pump 8. See fig. 1.
In practical application, the coagulated colloidal bubbles provided by the invention are preferably subjected to air flotation separation treatment on pollutants in a target water body directly in the form of coagulated colloidal bubble suspension obtained after stirring in the bubble generation unit. In the invention, the flow rate of the wastewater injected into the contact tank 3 is preferably 1083-4750 mL/min, and more preferably 2300-3500 mL/min. In the invention, the flow ratio of the coagulation type colloid bubble suspension to the wastewater is preferably (1-3): 5, specifically 1: 5. 2: 5 or 3: 5. in the present invention, the flow rate of the clear liquid discharged from the air-flotation clear liquid outlet 15 is preferably 50% to 70%, and more preferably 55% to 65% of the total flow rate of the wastewater and the coagulated colloidal bubble suspension. In the present invention, the flow rate of the scum discharged from the scum groove slag outlet 16 is preferably 30 to 50 percent, more preferably 35 to 45 percent of the total flow rate of the wastewater and the coagulated colloidal bubble suspension; in actual production, the flow rate of the scum discharged from the scum trough slag outlet 16 is specifically the total flow rate of the wastewater and the coagulated colloidal bubble suspension minus the flow rate of the clear liquid discharged from the air floatation clear liquid outlet 15.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 60mg/L (in terms of Al)2O3Metering) polyaluminum chloride (PACl) and 109mg/L dodecyl dimethyl betaine are mixed, and stirred for 5min under the condition that the stirring speed is 40rpm to obtain a bubble generation liquid;
(2) and (2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 33mL/min, and stirring is carried out for 80s under the condition that the stirring speed is 6000rpm, so as to obtain the PACl-coagulation type colloidal bubbles.
The polyaluminium chloride in the step (1) is omitted, and the common dodecyl dimethyl betaine colloid bubble is prepared according to the same method.
The products prepared after the completion of the stirring in step (2) in example 1 were actually PACl-coagulated colloid bubble suspensions and ordinary dodecyl dimethyl betaine colloid bubble suspensions, and the PACl-coagulated colloid bubble suspensions and ordinary dodecyl dimethyl betaine colloid bubble suspensions were subjected to liquid discharge kinetic tests: and (2) rapidly introducing the newly prepared colloid bubble suspension to be detected into the measuring cylinder at room temperature, timing by using an electronic stopwatch, discharging the colloid bubble liquid until the liquid volume at the bottom of the measuring cylinder is increased after the colloid bubble liquid is broken along with the increase of time, and stopping timing when the colloid bubble in the colloid bubble suspension to be detected is completely broken.
The life cycle of the colloid bubbles is the time from generation of the colloid bubbles to complete liquid drainage. The experimental result shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is about 128s, while the life cycle of the PACl-coagulation type colloid bubble provided by the invention is about 157s, and compared with the common dodecyl dimethyl betaine colloid bubble, the life cycle is improved by about 23%.
The initial total volume of the colloidal bubble suspension to be measured is V0The final total volume of liquid obtained at full drainage is VtThen, the gas content of the colloidal bubble is calculated by formula I:
the experimental result shows that the air content of the common dodecyl dimethyl betaine colloid bubble is 29-43%, while the air content of the PACl-coagulated colloid bubble provided by the invention is 53-55%, which is obviously higher than that of the common dodecyl dimethyl betaine colloid bubble.
The bubble diameter of the colloid bubble is measured by adopting a Mastersizer3000 laser particle sizer of British Mark company, and the result shows that the diameter of the common dodecyl dimethyl betaine colloid bubble is 50-60 mu m, while the diameter of the PACl-coagulation type colloid bubble provided by the invention is 35-45 mu m, which is obviously smaller than that of the common dodecyl dimethyl betaine colloid bubble.
In conclusion, the PACl-coagulation type colloidal bubbles provided by the invention have the advantages of long life cycle, high gas content and small diameter, and the PACl-coagulation type colloidal bubbles provided by the invention have better stability.
The PACl-coagulation type colloid bubble provided by the invention is subjected to surface charge test, and the result shows that the surface of the PACl-coagulation type colloid bubble is positively charged. The PACl-coagulated colloid bubble suspension prepared in the example 1 is directly used for treating nano wastewater (containing nano silicon dioxide with negative surface charge and SiO) in a continuous process of bubble generation-air flotation separation21400mg/L) is measured, and after the operation is stable, when the flow ratio of the nano wastewater to the PACl-coagulation type colloid bubble suspension is 5: 3. the actual dosage of PACl is 22.5mg/L (in terms of Al)2O3Measured), when the Hydraulic Retention Time (HRT) is 4.5min, the removal rate of the nano silicon dioxide can reach 88%. The common dodecyl dimethyl betaine colloid bubble suspension prepared in the embodiment 1 is used for treating the same nano wastewater in a 'coagulation-air flotation separation' continuous process, specifically, the nano wastewater to be treated is pre-stirred at 250rpm for 30s, a coagulant PACl is added, then the nano wastewater is stirred at 200rpm for 1min, then the nano wastewater is stirred at 40rpm for 10min, and finally the common dodecyl dimethyl betaine colloid bubble suspension is introduced for floatation separation for 4.5min, wherein the flow ratio of the nano wastewater to the common dodecyl dimethyl betaine colloid bubble suspension is 5: 3; if the sewage treatment effect equivalent to that of the 'bubble generation-air flotation separation' method is to be achieved, the PACl dosage is at least 38.1mg/L (Al is used) when the 'coagulation-air flotation separation' method is adopted2O3Meter). Compared with the prior art, under the condition of equivalent sewage treatment effect, the PACl-coagulation type colloidal bubble suspension provided by the invention is used for the process of bubble generation-air flotation separation, the dosage is less, and the treatment time is short.
After the PACl-coagulation type colloidal bubble suspension prepared in the example 1 is used for treating nano wastewater in a continuous process of bubble generation-air flotation separation, the content of residual Al in air flotation clear liquid discharged from an air flotation clear liquid water outlet is measured by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES), the content is converted into the amount of residual PACl, and the amount is compared with the actual adding amount of PACl, so that the result shows that more than 95 percent of PACl participates in the air flotation separation process; and (3) measuring the content of soluble organic carbon (DOC) in the air flotation clear liquid, wherein the result shows that the content of DOC in the air flotation clear liquid is not increased.
Example 2
(1) 4.0mg/L (as Al)2O3Metering) polyaluminum chloride (PACl) and 44mg/L dodecyl dimethyl betaine are mixed and stirred for 6min under the condition that the stirring speed is 30rpm, so as to obtain a bubble generation liquid;
(2) and (2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 30mL/min, and stirring is carried out for 90s under the condition that the stirring speed is 5000rpm, so as to obtain the PACl-coagulation type colloidal bubbles.
The polyaluminium chloride in the step (1) is omitted, and the common dodecyl dimethyl betaine colloid bubble is prepared according to the same method.
According to the method in the embodiment 1, the liquid discharge dynamics test of the PACl-coagulated colloid bubble suspension prepared in the embodiment 2 and the common dodecyl dimethyl betaine colloid bubble suspension shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is about 108s, while the life cycle of the PACl-coagulated colloid bubble provided by the invention is about 179s, which is about 33% higher than that of the common dodecyl dimethyl betaine colloid bubble, and thus, the PACl-coagulated colloid bubble provided by the invention has better stability.
The PACl-coagulation type colloid bubble provided by the invention is subjected to surface charge test, and the result shows that the surface of the PACl-coagulation type colloid bubble is positively charged. The PACl-coagulated colloid bubble suspension prepared in the example 2 is directly used for treating nano wastewater (containing nano silicon dioxide with negative surface charge and SiO) in the continuous process of bubble generation-air flotation separation297mg/L) is calculated, and after the operation is stable, under the same hydraulic conditions and operation conditions as those of example 1, when the actual dosage of PACl is 1.5mg/L (calculated as Al)2O3Meter) time, nano twoThe removal rate of the silicon oxide can reach 80 percent; compared with the coagulation-air flotation separation process under the same hydraulic conditions and treatment effects, the actual dosage of PACl is reduced by about 15%.
Example 3
(1) 1344mg/L (calculated as Fe (III)) of iron chloride (FeCl)3) Mixing with 109mg/L dodecyl dimethyl betaine, and stirring at 50rpm for 4min to obtain bubble generation solution;
(2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 35mL/min, and stirring for 60s under the condition that the stirring speed is 8000rpm to obtain FeCl3-coagulated colloidal bubbles.
And (3) omitting ferric chloride in the step (1), and preparing the common dodecyl dimethyl betaine colloid bubbles according to the same method.
FeCl prepared in example 3 was added in the same manner as in example 13The liquid discharge dynamics test of the coagulation type colloid bubble suspension and the common dodecyl dimethyl betaine colloid bubble suspension shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is about 132s, but the FeCl provided by the invention3The life cycle of the coagulation type colloidal bubbles is about 190s, and compared with the common dodecyl dimethyl betaine colloidal bubbles, the life cycle is improved by about 44%, which shows that the FeCl provided by the invention3The coagulation type colloidal bubbles have better stability.
For FeCl provided by the invention3Surface charge test of coagulated colloidal bubbles, results show that the FeCl3The surface of the coagulated colloidal bubbles is positively charged. FeCl prepared in example 33The coagulation type colloid bubble suspension is directly used for treating the effluent of alcohol wastewater biochemical treatment in a continuous process of bubble generation-air flotation separation (the chroma is about 960 black increase, and the content of soluble organic carbon DOC is about 197mg/L), and the effects of decoloring and removing organic matters are examined. After the operation is stable, when the pH value of the wastewater is 7.0, the wastewater and FeCl3-flow ratio of coagulated colloid bubble suspension is 3:1, FeCl3The actual dosage of (b) is 336mg/L (calculated as Fe (III)) and the Hydraulic Retention Time (HRT) isAnd 4min later, the chroma removal rate can reach 93%, and the DOC removal rate can reach 70%. Adopts the 'coagulation-precipitation' process to treat the same alcohol wastewater biochemical treatment effluent, specifically stirs the wastewater to be treated for 30s at 250rpm in advance, adds coagulant FeCl3Stirring is carried out again at 200rpm for 1min, then at 40rpm for 10min, and after 20min of precipitation, the supernatant is taken for DOC and color determination. In coagulant FeCl3Under the condition of the same dosage, the decoloration rate and DOC removal rate of the coagulation-precipitation process are only 68 percent and 48 percent; if the treatment effect equivalent to that of the 'bubble generation-air flotation separation' method is achieved, FeCl is generated in the 'coagulation-precipitation' process3The dosage of (b) is at least 840mg/L (calculated as Fe (III)). As can be seen, in the case of equivalent sewage treatment effect, FeCl provided by the present invention3The coagulation type colloid bubble suspension is used for the processes of bubble generation and air flotation separation, the dosage is small, and the processing time is short.
Example 4
(1) 1680mg/L (calculated as Fe (III)) of ferric chloride (FeCl)3) Mixing with 109mg/L dodecyl dimethyl betaine, and stirring at 50rpm for 4min to obtain bubble generation solution;
(2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 35mL/min, and stirring for 60s under the condition that the stirring speed is 8000rpm to obtain FeCl3-coagulated colloidal bubbles.
And (3) omitting ferric chloride in the step (1), and preparing the common dodecyl dimethyl betaine colloid bubbles according to the same method.
FeCl prepared in example 4 was added in the same manner as in example 13The liquid discharge dynamics test of the coagulation type colloid bubble suspension and the common dodecyl dimethyl betaine colloid bubble suspension shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is about 125s, but the FeCl provided by the invention3The life cycle of the coagulation type colloidal bubbles is about 176s, and compared with the common dodecyl dimethyl betaine colloidal bubbles, the life cycle is improved by about 41 percent, which shows that the FeCl provided by the invention3The coagulation type colloidal bubbles have better stability.
For FeCl provided by the invention3Surface charge test of coagulated colloidal bubbles, results show that the FeCl3The surface of the coagulated colloidal bubbles is positively charged. FeCl prepared in example 43The coagulated colloid bubble suspension was used directly in the "bubble generation-flotation separation" continuous process for treating the wastewater of example 3. After the run was stabilized, FeCl was added under the same hydraulic and operating conditions as in example 33When the actual dosage is 420mg/L (calculated by Fe (III)), the chroma removal rate can reach 85 percent, and the DOC removal rate can reach 78 percent; the decoloration rate and DOC removal rate in the coagulation-precipitation process are only 75% and 56% under the same dosage.
Example 5
(1) 1344mg/L (calculated as Fe (III)) of iron chloride (FeCl)3) Mixing with 109mg/L dodecyl dimethyl betaine, and stirring at 50rpm for 4min to obtain bubble generation solution;
(2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 35mL/min, and stirring for 60s under the condition that the stirring speed is 8000rpm to obtain FeCl3-coagulated colloidal bubbles.
And (3) omitting ferric chloride in the step (1), and preparing the common dodecyl dimethyl betaine colloid bubbles according to the same method.
FeCl prepared in example 5 was added in the same manner as in example 13The liquid discharge dynamics test of the coagulation type colloid bubble suspension and the common dodecyl dimethyl betaine colloid bubble suspension shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is 132s, but the FeCl provided by the invention3The life cycle of the coagulation type colloid bubble is 190s, and compared with the common dodecyl dimethyl betaine colloid bubble, the life cycle is improved by about 44 percent, which indicates that the FeCl provided by the invention3The coagulation type colloidal bubbles have better stability.
For FeCl provided by the invention3Surface charge test of coagulated colloidal bubbles, results show that the FeCl3-coagulated colloidal bubble surfaceIs positively charged. FeCl prepared in example 53The coagulated colloid bubble suspension was used directly in the "bubble generation-flotation separation" continuous process for treating the wastewater of example 3. After the operation is stable, when the pH value of the wastewater is 9.0, FeCl is added under the same hydraulic conditions and operation conditions as those of example 33When the actual dosage is 336mg/L (calculated by Fe (III)), the chroma removal rate can reach 88 percent, and the DOC removal rate can reach 75 percent; the decoloration rate and DOC removal rate in the coagulation-precipitation process are only 70 percent and 57 percent under the same dosage.
Example 6
(1) 1344mg/L (calculated as Fe (III)) of iron chloride (FeCl)3) Mixing with 109mg/L dodecyl dimethyl betaine, and stirring at 50rpm for 4min to obtain bubble generation solution;
(2) introducing air into the bubble generation liquid obtained in the step (1), wherein the flow rate of the introduced air is 35mL/min, and stirring for 60s under the condition that the stirring speed is 8000rpm to obtain FeCl3-coagulated colloidal bubbles.
And (3) omitting ferric chloride in the step (1), and preparing the common dodecyl dimethyl betaine colloid bubbles according to the same method.
FeCl prepared in example 6 was added in the same manner as in example 13The liquid discharge dynamics test of the coagulation type colloid bubble suspension and the common dodecyl dimethyl betaine colloid bubble suspension shows that the life cycle of the common dodecyl dimethyl betaine colloid bubble is 132s, but the FeCl provided by the invention3The life cycle of the coagulation type colloid bubble is 190s, and compared with the common dodecyl dimethyl betaine colloid bubble, the life cycle is improved by about 44 percent, which indicates that the FeCl provided by the invention3The coagulation type colloidal bubbles have better stability.
For FeCl provided by the invention3Surface charge test of coagulated colloidal bubbles, results show that the FeCl3The surface of the coagulated colloidal bubbles is positively charged. FeCl prepared in example 63Direct application of coagulated colloid bubble suspensions to the continuous "bubble Generation-flotation separation" Process example 3The wastewater of (2). After the operation is stable, when the pH value of the wastewater is 5.0, FeCl is added under the same hydraulic conditions and operation conditions as those of example 33When the actual dosage is 336mg/L (calculated by Fe (III)), the chroma removal rate can reach 72 percent, and the DOC removal rate can reach 61 percent; the decoloration rate and DOC removal rate in the coagulation-precipitation process are only 65% and 49% under the same dosage.
Example 7
The critical micelle concentration of a mixed solution of an amphoteric surfactant, such as dodecyl dimethyl betaine (BS-12), and a coagulant, such as PACl or FeCl, and the critical micelle concentration of the amphoteric surfactant were measured3And non-ionic polyacrylamides, for example; the solution to be detected is specifically:
solution I: a BS-12 aqueous solution, wherein the mass concentration range of BS-12 is 9.8-2508.2 mg/L;
solution II: the mixed water solution of BS-12 and PACl, wherein the mass concentration of BS-12 is 9.8-2508.2 mg/L, and the mass concentration of PACl is 1.3mg/L (by Al)2O3A meter);
solution III: BS-12 and FeCl3The mixed aqueous solution of (1), wherein the mass concentration of BS-12 is 9.8-2508.2 mg/L, and FeCl3The mass concentration of (b) is 224mg/L (calculated as Fe (III));
solution IV: the mixed aqueous solution of BS-12 and nonionic polyacrylamide is characterized in that the mass concentration of the BS-12 is 9.8-2508.2 mg/L, and the mass concentration of the nonionic polyacrylamide is 3 mg/L.
The critical micelle concentrations of the solutions I to IV are tested by a surface tension method at room temperature, the mass concentration of the corresponding BS-12 is the critical micelle concentration when the surface tension reaches the lowest value, and the experimental result is shown in table 1, wherein the critical micelle concentration (mg/L) and the corresponding molar concentration (mmol/L) are measured by the mass concentration meter of the BS-12 in table 1. As can be seen from table 1, the critical micelle concentration of the mixed solution obtained by mixing the BS-12 and the coagulant is significantly higher than that of the BS-12, which can ensure that the usable concentration range (based on the molar concentration of BS-12) of the bubble generating liquid provided by the present invention is wider, and further expand the usable range of the coagulated colloidal bubbles provided by the present invention.
TABLE 1 critical micelle concentration of BS-12 and mixed solution of BS-12 and coagulant and BS-12
Solution to be tested Critical micelle concentration (mg/L) Molarity (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
As can be seen from the above examples and test results, the life cycle (drainage time) of the coagulated colloidal bubbles prepared by the method provided by the invention is long and is 142-200 s; the gas content is high and is 53-55%; the average diameter of the coagulated colloid bubbles is small and is 35-45 mu m; can be used in a wider pH range (such as FeCl)3pH value range applicable to coagulation type colloidal bubbles5-9) has better removal effect on target pollutants. The method can ensure that the coagulation type colloidal bubbles keep stable in the continuous process of air floatation separation, and improve the treatment effect on sewage. The coagulation type colloid bubble provided by the invention is applied to actual sewage treatment, compared with other air floatation technologies, the coagulation type colloid bubble can increase the specific surface area of a medicament contacted with a target pollutant, effectively remove the target pollutant in a targeted manner, reduce the hydraulic retention time, and obviously reduce the dosage while improving the pollutant removal efficiency; a chemical feeding link does not need to be independently arranged, so that the occupied area and the cost of the treatment process are saved; the treatment efficiency is remarkably improved, the effect is enhanced, the dosage is greatly reduced, the dosage cost is saved, the organic pollution of water body caused by excessive dosage of the medicine is avoided, and the application in the field of wastewater treatment is strong.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A preparation method of coagulation type colloid bubbles comprises the following steps:
(1) mixing an amphoteric surfactant and a coagulant to obtain a bubble generation liquid; the amphoteric surfactant is dodecyl dimethyl betaine;
(2) introducing air into the bubble generation liquid obtained in the step (1), and stirring for 60-90 s under the condition that the stirring speed is 5000-8000 rpm to obtain the coagulated colloidal bubbles; the volume ratio of the flow of the introduced air to the bubble generation liquid is (30-67) mL/min: 2000 mL;
the coagulant in the step (1) comprises a metal salt coagulant, an inorganic polymer coagulant or an organic polymer flocculant;
the metal salt coagulant comprises FeCl3、AlCl3Or KAl (SO)4)2·12H2O, the mass ratio of the metal salt coagulant to the amphoteric surfactant is (9.9-21.6): 1.0;
the inorganic polymer coagulant comprises polyaluminium chloride or polyferric chloride, and the mass ratio of the inorganic polymer coagulant to the amphoteric surfactant is (0.3-1.2): 1.0;
the organic polymer flocculant comprises nonionic polyacrylamide or ionic polyacrylamide, and the mass ratio of the organic polymer flocculant to the amphoteric surfactant is (0.2-1.8): 1.0;
the life cycle of the coagulated colloid bubbles is 142-200 s, the gas content is 53-55%, and the average diameter is 35-45 μm.
2. The device for implementing the preparation method according to claim 1, comprising a bubble generation liquid storage and a bubble generation unit, wherein the bubble generation unit (2) is provided with a bubble generation liquid inlet (11) and a coagulation type colloid bubble liquid outlet (12), the top of the bubble generation unit (2) is provided with a high-speed stirrer (5), the bottom of the bubble generation unit (2) is provided with an air inlet (10), the air inlet (10) is communicated with a gas flowmeter (9), and the inner wall of the bubble generation unit (2) is provided with a baffle.
3. The apparatus of claim 2, wherein when the number of baffles is greater than 1, the baffles are equally spaced.
4. A device according to claim 2 or 3, characterized in that the top of the bubble generating liquid storage (1) is provided with a stirrer (6), and the bubble generating liquid storage is communicated with the bubble generating liquid inlet (11) through a water pump (7).
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