CN212924503U - Two-membrane three-phase integrated device for ammonia nitrogen wastewater treatment - Google Patents
Two-membrane three-phase integrated device for ammonia nitrogen wastewater treatment Download PDFInfo
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- CN212924503U CN212924503U CN202022020044.4U CN202022020044U CN212924503U CN 212924503 U CN212924503 U CN 212924503U CN 202022020044 U CN202022020044 U CN 202022020044U CN 212924503 U CN212924503 U CN 212924503U
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Abstract
The utility model discloses a two membrane three-phase integrated device for ammonia nitrogen wastewater treatment belongs to ammonia nitrogen wastewater membrane technical treatment field. The two-membrane three-phase integrated device comprises a conductive membrane, a hydrophobic membrane, an electrocoagulation phase, a deamination phase and an ammonia recovery phase, wastewater is flocculated by flocs generated by an anode in the electrocoagulation phase, and organic matters are removed after the wastewater is filtered by a cathode conductive membrane; the effluent of the conductive film is alkaline, ammonium ions in the wastewater are converted into free ammonia molecules, the ammonia molecules are deaminated by a hydrophobic film in a deamination phase, the produced water is collected, and the ammonia molecules are recovered by acid liquor in an ammonia recovery phase. Compared with the traditional electric flocculation reactor, the utility model realizes the synchronous flocculation and filtration interception of organic pollutants, and obviously improves the effluent quality; compared with the independent membrane deamination process, the utility model discloses need not add alkaline medicament, economic environmental protection. The utility model discloses can realize getting rid of organic matter and deamination in step, the flexible operation, area is little, and easily control is fit for the industrialization and popularizes and applies.
Description
[ technical field ] A method for producing a semiconductor device
The utility model belongs to ammonia nitrogen waste water membrane technical treatment field, concretely relates to two membrane three-phase integrated device for ammonia nitrogen waste water treatment.
[ background of the invention ]
The ammonia nitrogen wastewater mainly comes from coking, petrifaction, animal husbandry, chemical fertilizers, dairy product production, refuse landfill and the like, and the excessive existence of the ammonia nitrogen wastewater in the water body can cause serious harm to organisms and living environment thereof, such as water body eutrophication, black and odorous water body formation and the like. Typical treatment techniques include physical and chemical methods, biological methods, and membrane separation techniques. The physical and chemical methods comprise a chemical precipitation method, an ammonia nitrogen stripping method, a selective ion exchange method, a breakpoint chlorine adding method and the like. The chemical precipitation method is simple in process and high in efficiency, but needs to be added with medicaments and has the pollution problem of chloride ions and phosphorus; the ammonia nitrogen stripping method has good and stable treatment effect, can recycle ammonia nitrogen, but is greatly influenced by environmental temperature, has limited stripping capacity, large power consumption and the like; the selective ion exchange treatment capacity is limited, and the regeneration and utilization process is complex; the breakpoint chlorination method is suitable for treating low-concentration ammonia nitrogen wastewater, and requires higher chlorine adding amount and higher treatment cost. The biological method has high cost and limited deamination efficiency. The membrane separation has the advantages of wide application range, high removal rate, low cost, simple operation and the like, is a method for treating ammonia nitrogen wastewater with higher potential at present, and has the influence on the stability and treatment effect of a system due to the problem of membrane pollution. The ammonia nitrogen wastewater contains organic matters, ammonia nitrogen and the like, a single treatment technology can only remove partial pollutants to a certain extent, and effective removal of the pollutants in the wastewater is difficult to ensure.
In general, electroflocculation is an effective method for treating organic wastewater, but the effluent of electroflocculation sometimes still has micro-flocs and the like, and membrane treatment is needed to improve the effluent quality. If the cathode of the electric flocculation is a conductive film, flocs can be trapped to improve the effluent quality, and meanwhile, the cathode can generate electrostatic repulsion on pollutants, and water electrolysis can generate nano microbubbles to wash the surface of the membrane, so that the membrane has a good anti-pollution effect; on the other hand, the water outlet of the conducting film is alkaline due to the electrolysis of cathode water, and ammonium ions in the wastewater can be converted into free ammonia molecules.
Therefore, if can introduce the electric flocculation reactor with the conducting film and carry out the integration with hydrophobic membrane deamination, can realize alleviating the membrane pollution when getting rid of organic matter, the ammonium ion in the waste water turns into the ammonia molecule of free state in addition, through hydrophobic membrane deamination device deamination, can effectively get rid of the ammonia nitrogen in the waste water, need not plus alkaline medicament, reduces waste water treatment's cost and improves the validity of handling. So far, no report exists for treating ammonia nitrogen wastewater by introducing a conductive film into an electric flocculation reactor and integrating the conductive film with a hydrophobic film deamination.
[ Utility model ] content
The utility model aims at providing a two membrane three-phase integrated device for ammonia nitrogen waste water treatment, aim at combining organic matter and ammonia nitrogen in the conducting film, electric flocculation, the respective advantage of technique of membrane deamination come the desorption waste water, overcome the defect that single processing technology handled ammonia nitrogen waste water.
In order to realize the purpose of the utility model, the utility model adopts the following technical scheme:
a two-membrane three-phase integrated device for ammonia nitrogen wastewater treatment comprises a conductive membrane (1-3), a hydrophobic membrane (1-4), an electric flocculation phase (1-5), a deamination phase (1-6) and an ammonia recovery phase (1-7), wherein the electric flocculation phase (1-5), the deamination phase (1-6) and the ammonia recovery phase (1-7) are connected with the conductive membrane (1-4) through the conductive membrane (1-3) and the hydrophobic membrane (1-4), a conductive membrane assembly is formed by a second organic glass frame (1-1-2), an anode (1-2) and the conductive membrane assembly are kept at a certain distance and immersed in a raw water tank (7) and are connected through a direct current power supply (2) to form an electric flocculation tank (1);
the electroflocculation phase (1-5) is formed by fixing an anode (1-2) and a conductive film (1-3), namely a cathode, through a first organic glass frame (1-1-1); the raw water in the raw water tank (7) is led into the electric flocculation tank (1) through a first peristaltic pump (8-1), and the water in the electric flocculation tank (1) is led out through a fourth peristaltic pump (8-4) to form a cross flow flowing state on the surface of a cathode; the anode (1-2) and the cathode are respectively connected to the anode and the cathode of the direct current power supply (2) through leads;
the deamination phase (1-6) is formed by fixing a cathode and a hydrophobic membrane (1-4) through a second organic glass frame (1-1-2); the effluent of the cathode enters a deamination phase (1-6), is connected with a vacuum meter (3) and a pH meter (4) through a silicone tube, and is guided into a collector (6) through a third peristaltic pump (8-3);
the ammonia recovery phase (1-7) is composed of a hydrophobic membrane (1-4) and a second organic glass frame (1-1-2); ammonia gas molecules penetrating through the hydrophobic membrane enter an ammonia recovery phase (1-7) and are contacted with acid absorption liquid of an acid tank (5) through a second peristaltic pump (8-2) and recovered, and the ammonia recovery phase (1-7) and the acid tank (5) are integrally formed into a hydrophobic membrane deamination device (9).
Preferably, the anode material is at least one of iron, aluminum or iron-aluminum composite material.
Preferably, the cathode material of the conductive film is prepared by dispersing Carbon Nanotubes (CNTs) in N-methylpyrrolidone (NMP), taking polyvinylidene fluoride (PVDF) as a polymer, taking a stainless steel net as a substrate and taking lithium chloride (LiCl) as an additive through a phase inversion method.
The utility model discloses utilize two membrane three-phase integrated devices to carry out the processing of ammonia nitrogen waste water, its principle is:
the ammonia nitrogen wastewater is pumped into an electric flocculation tank, the electric flocculation process is carried out after the electric flocculation tank is powered on, iron ions and aluminum ions generated by anode electrolysis form flocs, organic matters in the wastewater form precipitates after flocculation, the precipitates are filtered by a cathode conductive film, and membrane filtered water enters a deamination phase. The conductive film is used as a cathode, and on one hand, the conductive film has better anti-pollution effect due to the electrostatic repulsion and generated nanometer micro-bubbles to scour the surface of the film; on the other hand, the water outlet of the conducting film is alkaline due to the electrolysis of cathode water, ammonium ions are converted into free ammonia molecules in the deamination phase, the ammonia molecules are deaminated in the deamination phase through the hydrophobic film, the produced water is collected, and the ammonia molecules enter the ammonia recovery phase through the hydrophobic film to be absorbed by acid liquor, so that the ammonia recovery is realized.
Compared with the prior art, the beneficial effects of the utility model are that:
the utility model discloses carry out the integration with electric flocculation reactor and hydrophobic membrane deamination for the first time and handle ammonia nitrogen waste water. Compared with the traditional electric flocculation reactor, the utility model uses the conductive film as the cathode, can realize the synchronous flocculation and filtration interception of organic pollutants, avoids the secondary treatment of membrane filtration after the electric flocculation, and has better anti-pollution function by using the conductive film as the cathode; compared with the independent membrane deamination process, the utility model discloses need not add alkaline medicament, the simple and economic environmental protection of process. The utility model discloses can realize simultaneously that the high efficiency of organic matter in the ammonia nitrogen waste water is got rid of and the green of ammonia is retrieved, need not plus medicament, easily control, the flexible operation, area is little, is fit for the industrialization and popularizes and applies.
[ description of the drawings ]
FIG. 1 is a schematic structural view of a two-film three-phase integrated device according to the present invention;
FIG. 2 is a layout diagram of the components in two-film three-phase of the present invention;
FIG. 3 is a schematic diagram of mass transfer for a two-membrane three-phase process of the present invention;
reference numbers in the figures: 1, an electric flocculation tank; 1-1-1 a first plexiglass frame; 1-1-2 second plexiglass frame; 1-2 anodes; 1-3 conductive films; 1-4 hydrophobic membranes; 1-5 electroflocculation phase; 1-6 deamination phase; 1-7 ammonia recovery phase; 2, a direct current power supply; 3, a vacuum meter; 4, a pH meter; 5, an acid tank; 6, a collector; 7, a raw water tank; 8-1 a first peristaltic pump; 8-2 a second peristaltic pump; 8-3 a third peristaltic pump; 8-4 a fourth peristaltic pump; 9 hydrophobic membrane deamination device.
[ detailed description ] embodiments
The principles and features of the present invention are described in connection with the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.
Embodiment 1A two membrane three-phase integrated device for ammonia nitrogen wastewater treatment
As shown in fig. 1, the integrated treatment device comprises a conductive film (1-3), a hydrophobic film (1-4), an electrocoagulation phase (1-5), a deamination phase (1-6) and an ammonia recovery phase (1-7), wherein the electrocoagulation phase (1-5), the deamination phase (1-6) and the ammonia recovery phase (1-7) are connected by the conductive film (1-3) and the hydrophobic film (1-4), a conductive film component is formed by a second organic glass frame (1-1-2), an anode (1-2) and the conductive film component are kept at a distance of 0.5cm and immersed in a raw water tank (7), and are connected by a direct current power supply (2) to form an electrocoagulation tank (1);
the electroflocculation phase (1-5) is formed by fixing an anode (1-2) and a conductive film (1-3), namely a cathode, through a first organic glass frame (1-1-1); the raw water is led into the electric flocculation tank (1) through a first peristaltic pump (8-1), and then the water in the electric flocculation tank (1) is led out through a fourth peristaltic pump (8-4), so that a cross flow state is formed on the surface of a cathode; the anode (1-2) and the cathode are respectively connected to the anode and the cathode of the direct current power supply (2) through leads;
the deamination phase (1-6) is fixed by a cathode and a hydrophobic membrane (1-4) through a second organic glass frame (1-1-2); the effluent of the cathode enters a deamination phase (1-6), is connected with a pressure gauge (3) and a pH meter (4) through a silica gel tube, and is guided into a collector (6) through a third peristaltic pump (8-3);
the ammonia recovery phase (1-7) is composed of a hydrophobic membrane (1-4) and a second organic glass frame (1-1-2); ammonia molecules penetrating through the hydrophobic membrane enter an ammonia recovery phase (1-7), and are contacted with an acid absorption liquid of the acid tank (5) through a second peristaltic pump (8-2) and recycled;
in this embodiment, the anode is an aluminum electrode, and the cathode conductive film is a self-made CNT/PVDF/stainless steel mesh conductive film; the preparation method comprises the following steps: first, 0.85 g of Carbon Nanotubes (CNTs) were dispersed in 80g of N-methylpyrrolidone (NMP) by an ultrasonic instrument for 30 min; then, slowly adding 17g of polyvinylidene fluoride (PVDF) and 3g of lithium chloride (LiCl) into the mixture, and stirring for 12 hours at the speed of 200rpm by using a cantilever stirrer to obtain a uniform membrane liquid; then, defoaming the membrane liquid for 6 hours by using a vacuum box; coating the film on a stainless steel net with the thickness of 250 mu m by using an automatic film scraper, and immersing the scraped film in a deionized water coagulation bath after exposing the film in air for 30 s; the film was immersed in water at room temperature for 24 hours to remove all solvents and then rinsed with deionized water prior to use;
the hydrophobic membrane is a Duarpore PVDF membrane produced by Millipore corporation of America, and the average pore diameter is 0.22 mu m; the anode andthe effective areas of the conductive film and the hydrophobic film are both 12cm2。
The acid absorption liquid is one of dilute sulfuric acid, dilute hydrochloric acid and dilute nitric acid.
The concentration of the acid absorption liquid is 0.05-0.5 mol/L.
The current density is 5A/m2-50A/m2。
The pressure on the conductive film is 0.3-1.2 bar.
The pH range of the cathode effluent is 10-12.
The current density of the direct current power supply (2) is regulated to regulate the anode flocculation effect; the pH value of cathode effluent is adjusted by regulating and controlling the current density of the direct current power supply (2) and the third peristaltic pump (8-3); the circulation of the ammonia nitrogen wastewater in the electric flocculation tank (1) is regulated and controlled by regulating the first peristaltic pump (8-1) and the fourth peristaltic pump (8-4), so that a good cross flow effect is formed on the surface of the cathode; the liquid flow speeds of the deamination phases (1-6) and the ammonia recovery phases (1-7) are regulated and controlled by adjusting the second peristaltic pump (8-2) and the third peristaltic pump (8-3), so that a better deamination effect is realized in the deamination phases, and a better recovery effect is realized in the ammonia recovery phases.
Example 2 Ammonia nitrogen wastewater is treated by the integrated device in example 1
Adding 1.5L of ammonia nitrogen wastewater (with the components of 100mg/L humic acid, 200mg/L ammonium chloride and 100mmol/L sodium chloride) into a 2L raw water tank and a 2L electric flocculation tank respectively; 500mL of 0.3mol/L sulfuric acid solution is added into a 1L acid tank;
starting a first peristaltic pump 8-1 and a fourth peristaltic pump 8-4, and controlling the flow rate to be 50 mL/min; starting a second peristaltic pump 8-2 of the acid tank, controlling the flow rate to be 100mL/min for circulation, and removing bubbles in the device;
the DC power supply 2 is turned on to control the current density to be 20A/m2And starting the third peristaltic pump 8-3, controlling the flow rate to be 100mL/min, controlling the alkalinity of the effluent of the conductive film to be more than 10, and controlling the pressure on the conductive film to be 0.3-1.2 bar.
In this example, the organic matter and ammonia nitrogen removal rate of the produced water were detected at different times, each set of experiments was tested 3 times, and the average values of the COD removal rate and ammonia nitrogen removal rate of the produced water are shown in table 1.
TABLE 1. COD removal rate of produced water and ammonia nitrogen removal rate as a function of time
As can be seen from Table 1, the COD removal rate of the wastewater increased with the increase of the operation time, and the removal rate of the organic matters of the integrated device reached more than 90% after the operation time increased to 60 minutes.
Along with the increase of time, the removal rate of ammonia nitrogen has no obvious change trend, which shows that the device has good stability, and the pH value of the conducting film effluent is stabilized to be more than 10.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered by the present invention.
Claims (3)
1. A two-membrane three-phase integrated device for ammonia nitrogen wastewater treatment is characterized by comprising a conductive membrane (1-3), a hydrophobic membrane (1-4), an electric flocculation phase (1-5), a deamination phase (1-6) and an ammonia recovery phase (1-7), wherein the electric flocculation phase (1-5), the deamination phase (1-6) and the ammonia recovery phase (1-7) are connected through the conductive membrane (1-3) and the hydrophobic membrane (1-4), a conductive membrane assembly is formed through a second organic glass frame (1-1-2), an anode (1-2) and the conductive membrane assembly are kept at a certain distance and immersed in a raw water tank (7), and are connected through a direct current power supply (2) to form an electric flocculation tank (1);
the electroflocculation phase (1-5) is formed by fixing an anode (1-2) and a conductive film (1-3), namely a cathode, through a first organic glass frame (1-1-1); the raw water in the raw water tank (7) is led into the electric flocculation tank (1) through a first peristaltic pump (8-1), and the water in the electric flocculation tank (1) is led out through a fourth peristaltic pump (8-4) to form a cross flow flowing state on the surface of a cathode; the anode (1-2) and the cathode are respectively connected to the anode and the cathode of the direct current power supply (2) through leads;
the deamination phase (1-6) is formed by fixing a cathode and a hydrophobic membrane (1-4) through a second organic glass frame (1-1-2); the effluent of the cathode enters a deamination phase (1-6), is connected with a vacuum meter (3) and a pH meter (4) through a silicone tube, and is guided into a collector (6) through a third peristaltic pump (8-3);
the ammonia recovery phase (1-7) is composed of a hydrophobic membrane (1-4) and a second organic glass frame (1-1-2); ammonia gas molecules penetrating through the hydrophobic membrane enter an ammonia recovery phase (1-7) and are contacted with acid absorption liquid of an acid tank (5) through a second peristaltic pump (8-2) and recovered, and the ammonia recovery phase (1-7) and the acid tank (5) are integrally formed into a hydrophobic membrane deamination device (9).
2. The two-film, three-phase integrated device according to claim 1, wherein the anode material is at least one of iron, aluminum or iron-aluminum composite.
3. The two-film three-phase integrated device according to claim 1, wherein the conductive film cathode material is prepared by dispersing Carbon Nanotubes (CNTs) in N-methylpyrrolidone (NMP), using polyvinylidene fluoride (PVDF) as a polymer, stainless steel mesh as a substrate, and lithium chloride (LiCl) as an additive through a phase inversion method.
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