CN111285448A - Organic wastewater treatment device and method with proton exchange membrane as carrier - Google Patents
Organic wastewater treatment device and method with proton exchange membrane as carrier Download PDFInfo
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Abstract
The invention discloses an organic wastewater treatment device and method taking a proton exchange membrane as a carrier, wherein the device comprises a reaction generator, and a proton exchange membrane element, a power supply and a controller which are arranged in the reaction generator; the working voltage range of the proton exchange membrane element required by electrolyzing the organic wastewater to be treated is determined after the degradation efficiency of organic matters in the organic wastewater and the energy consumption of electric energy are comprehensively considered, and in the treatment process of the organic wastewater, the working voltage of the proton exchange membrane element is reduced along with the reduction of the concentration of the organic matters in the organic wastewater in the reaction generator, so that the high-efficiency utilization of energy is realized.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to an organic wastewater treatment device and method with a proton exchange membrane as a carrier.
Background
The organic wastewater contains various carbohydrates, proteins, grease, lignin and the like, and the organic wastewater discharged by the industries of food processing, paper making and the like is more complex in components and difficult to degrade, so that the ecological system is eutrophicated, most aquatic organisms die, foul smell is generated, and the water quality and the environment are deteriorated.
The Fenton oxidation method is widely applied to the oxidation removal process of some particularly refractory organic matters such as high COD. As an advanced oxidation method for refractory organic matters in wastewater, the method utilizes the strong oxidation-reduction property of ferrous sulfate and hydrogen peroxide to react to generate hydroxyl radicals with strong oxidation property, thereby effectively oxidizing and decomposing the refractory organic matters.
Although the traditional Fenton oxidation method can oxidize and destroy various toxic and harmful organic matters and has wide application range, secondary pollutants are inevitably generated due to the introduction of a Fenton reagent; in addition, the method can not fully mineralize organic matters, although Fe is generated in the organic wastewater treatment process2+Is oxidized into Fe3+The coagulative precipitates are removed, but the initial substances are partially converted into some intermediate products, which are mixed with Fe3+Complex formation can affect the oxidation effect and cause greater harm to the environment; then, H2O2The utilization rate is not high, so that the treatment cost is high. The Fenton oxidation method is used as pretreatment or final advanced treatment of the organic wastewater difficult to degrade, and is combined with other treatment methods to treat the organic wastewater in practical application.
The proton exchange membrane is mainly applied to two aspects, on one hand, the water electrolysis process with the proton exchange membrane as a carrier is adopted, an anode catalyst is a single noble metal oxide, a cathode catalyst is platinum group metal and alloy thereof, and hydrogen can be produced cleanly, environmentally and efficiently, but the commercialization process is restricted due to the problems of high price of the noble metal catalyst and the membrane and the like; on the other hand, the proton exchange membrane is used for treating organic wastewater by utilizing the basic principle of the membrane fuel cell, and organic matters in the wastewater are used as 'fuel' in the membrane fuel cell, so that the purpose of degrading the organic matters is achieved, and the process is a process for converting chemical energy into electric energy.
Disclosure of Invention
The invention aims to provide an organic wastewater treatment device and method taking a proton exchange membrane as a carrier, the device does not need to introduce any reagent in the treatment process of organic wastewater, the cost is greatly reduced, secondary pollution is avoided, and the organic wastewater treatment method realizes high-efficiency utilization of energy while ensuring that organic matters in the organic wastewater are rapidly degraded.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an organic wastewater treatment device taking a proton exchange membrane as a carrier is characterized by comprising:
the device comprises a reaction generator, a water inlet and a water outlet, wherein the lower part of the reaction generator is provided with the water inlet, the upper part of the reaction generator is provided with the water outlet, a plurality of proton exchange membrane elements are arranged on the inner wall of the reaction generator at intervals from the water inlet to the water outlet, the proton exchange membrane elements have hollow structures, and the hollow structures are communicated with the outside of the reaction generator;
the side wall of the proton exchange membrane element sequentially comprises from outside to inside: an anode gas diffusion and current collection layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer, a cathode gas diffusion and current collection layer;
the proton exchange membrane element is connected with a direct current power supply, and the direct current power supply is electrically connected with a controller.
Preferably, the inner wall of the reaction generator is provided with a plurality of COD concentration detection probes, and the COD concentration detection probes are electrically connected with the controller.
Preferably, the proton exchange membrane elements are arranged on the inner wall of the reaction generator at intervals in a staggered manner to form Z-shaped flow channels.
Preferably, a COD concentration detection probe is arranged in the reaction generator corresponding to the flow channel on one side of each proton exchange membrane element.
Preferably, a flow regulating valve is arranged at the water inlet or the water outlet of the reaction generator.
Preferably, the proton exchange membrane element is flat.
Preferably, the anode gas diffusion and current collection layer is one or more layers of titanium mesh or titanium grid; the anode catalyst layer and the cathode catalyst layer are Pt/C electro-catalysts; the proton exchange membrane is a perfluorinated sulfonic acid polymer proton exchange membrane; the cathode gas diffusion and current collection layer is made of titanium, graphite or stainless steel.
The organic wastewater treatment method based on the organic wastewater treatment device with the proton exchange membrane as the carrier comprises the following steps:
1) determining the working voltage range required for electrolyzing the organic wastewater to be treated
Taking a certain amount of organic wastewater to be treated, measuring the concentration of organic matters of the organic wastewater, dividing the organic wastewater into N parts with the same quantity, putting the N parts into a reaction generator of an organic wastewater treatment device, electrolyzing each part of organic wastewater by a proton exchange membrane element respectively, wherein K is more than or equal to 1 and less than or equal to N, the working voltage of the proton exchange membrane element corresponding to each part of organic wastewater M (K) is U (K), sequentially increasing the working voltage of the proton exchange membrane element from U (1) to U (K), measuring the concentration of the organic matters in each part of organic wastewater after treating for the same time, calculating the degradation rate S (K) of the organic matters in each part of organic wastewater M (K) by dividing the treatment time by the concentration difference of the organic matters before and after each part of organic wastewater is treated, and then calculating the degradation rate acceleration of the:
wherein:
Δ (k): the degradation rate of organic matters in the kth to the kth plus 1 part of organic wastewater is increased, and the unit is ppm/hV;
s (k + 1): the degradation rate of organic matters in the k +1 part of organic wastewater is unit ppm/h;
s (k): the degradation rate of organic matters in the kth part of organic wastewater is unit ppm/h;
u (k + 1): working voltage of a proton exchange membrane element corresponding to the (k +1) th organic wastewater is unit V;
u (k): working voltage of a proton exchange membrane element corresponding to kth organic wastewater is unit V;
when the organic matter degradation rate is accelerated to the maximum, the corresponding working voltages of the proton exchange membrane elements are respectively U (k) and U (k +1), and then the working voltage range required by electrolyzing the organic wastewater to be treated is determined to be 90% U (k) to 110% U (k + 1);
2) treatment of waste water
Setting the working voltage of the proton exchange membrane element in the reaction generator within the working voltage range required for electrolyzing the organic wastewater to be treated determined in the step 1); the organic wastewater to be treated flows in from the water inlet of the reaction generator, is contacted with the electrified proton exchange membrane element in sequence to react, and flows out from the water outlet of the reaction generator.
Preferably, the working voltage of the proton exchange membrane element in the step 2) is reduced along with the reduction of the concentration of the organic matters in the organic wastewater in the reaction generator in the organic wastewater treatment process.
Preferably, the organic wastewater needs to be pretreated before entering the reaction generator, and the pretreatment is one or more of acid-base regulation, coagulation, precipitation, adsorption and filtration.
The invention relates to an organic wastewater treatment device and method with a proton exchange membrane as a carrier, wherein the device comprises the following steps:
according to the organic wastewater treatment device, the adopted membrane element is the proton exchange membrane element, and the proton exchange membrane element is used for treating organic wastewater, so that no pollutant is produced, and the subsequent treatment process is reduced; no reagent is additionally added in the treatment process, so that the cost is reduced, and secondary pollution is avoided.
The reaction mechanism when the proton exchange membrane element is used for treating the organic wastewater is as follows: the reaction of the anode (including anode gas diffusion and current collection layer and anode catalyst layer) of the proton exchange membrane element is as follows: 2H2O-2e-→2OH·+2H+(ii) a Proton (H)+) From the anode of the proton exchange membrane element to the cathode of the proton exchange membrane element through the proton exchange membraneReaching the cathode of the proton exchange membrane element (comprising a cathode gas diffusion and current collection layer and a cathode catalyst layer), wherein the reaction of the cathode of the proton exchange membrane element is as follows: 4H++4e-+O2→2H2O ≈ ≈ O ≈ er; hydroxyl radical (OH) generated by the anode of the proton exchange membrane element is a strong oxidant with the oxidation-reduction potential of 2.8V and the oxidability second to fluorine, and can react with organic matters in the organic wastewater to degrade and remove the organic matters in the organic wastewater, thereby achieving the purpose of treating the organic wastewater. The water vapor generated by the cathode of the proton exchange membrane element can be discharged out of the reaction generator in time through the hollow structure, thereby being beneficial to the continuous proceeding of the cathode reaction of the proton exchange membrane.
The anode gas diffusion and current collection layer of the proton exchange membrane element is one or more layers of titanium nets or titanium grids, and has the functions of supporting a catalyst layer, stabilizing the structure of the membrane element, providing a gas channel for reaction and the like; the catalyst of the anode catalyst layer and the cathode catalyst layer of the proton exchange membrane element is a Pt/C electrocatalyst, wherein the loading amount of Pt is 11-15 mg/cm2The anode of the proton exchange membrane element is an insoluble anode, so that the consumption of electrode materials does not exist in the organic wastewater treatment process, and the cost is saved; the proton exchange membrane in the proton exchange membrane element adopts a perfluorinated sulfonic acid polymer proton exchange membrane, and has the advantages of reduced voltage, high conductivity, high mechanical strength and the like.
The proton exchange membrane elements are arranged on the inner wall of the reaction generator at intervals and in a staggered manner to form Z-shaped flow channels, so that the contact time and the contact area of the organic wastewater and the proton exchange membrane elements are greatly increased, the reaction is as full as possible, the tangential flow formed by the organic wastewater and the surfaces of the proton exchange membrane elements has a certain scouring effect on the surfaces of the proton exchange membrane elements, and the deposition of pollutants on the surfaces of the proton exchange membrane elements is effectively inhibited.
The degradation rate of organic matters in the organic wastewater is not only related to the concentration of COD in the organic wastewater, but also related to the power supply voltage of a proton exchange membrane element, the degradation efficiency and the electric energy consumption of the organic matters in the organic wastewater are comprehensively considered, the working voltage range of the proton exchange membrane element required for electrolyzing the organic wastewater to be treated is determined, and the working voltage of the proton exchange membrane element is used for electrolyzing the organic wastewater to be treated in the range, so that the organic matters in the organic wastewater can be rapidly and effectively degraded, and the efficient utilization of energy can be realized.
In the organic wastewater treatment process, the working voltage of the proton exchange membrane element can be reduced according to the reduction of the concentration of organic matters in the organic wastewater in the reaction generator, energy can be saved and the efficient utilization of energy can be realized on the premise of ensuring that the organic matters in the organic wastewater are effectively degraded, because in the organic wastewater treatment process, the degradation rate of the organic matters is increased along with the increase of the working voltage of the proton exchange membrane element, and the acceleration of the degradation rate of the organic matters is firstly increased and then reduced along with the increase of the working voltage of the proton exchange membrane element.
In addition, the organic wastewater is pretreated before entering the reaction generator, so that the conventional easily-treated components in the organic wastewater are removed in a physical or chemical mode, the pertinence and the efficiency of removing the difficultly-degraded organic matters in the organic wastewater by using the method are improved, and the fouling of a proton exchange membrane element can be reduced.
The invention has the beneficial effects that:
the organic wastewater treatment device is based on a proton exchange membrane, and the device is used for carrying out electrochemical degradation on organic matters which are difficult to degrade in organic wastewater without generating any pollutant, so that the subsequent treatment process is reduced; in addition, the device is used for treating the organic wastewater, no reagent is additionally added, the cost is reduced, secondary pollution is avoided, and the treatment efficiency of the organic wastewater is improved.
The invention determines the working voltage range of the proton exchange membrane element required by electrolyzing the organic wastewater to be treated after comprehensively considering the degradation efficiency of organic matters in the organic wastewater and the energy consumption of electric energy, and reduces the working voltage of the proton exchange membrane element along with the reduction of the concentration of the organic matters in the organic wastewater in the reaction generator in the treatment process of the organic wastewater, thereby realizing the high-efficiency utilization of energy.
The anode of the proton exchange membrane element adopted by the invention is an insoluble anode, so that the consumption of electrode materials is avoided in the organic wastewater treatment process, and the cost is saved.
Drawings
FIG. 1 is a schematic side sectional view of a reaction generator according to example 1 of the present invention.
FIG. 2 is a schematic diagram of the installation of one of the proton exchange membrane elements in a reactor in a plan view of the reactor of example 1 of the present invention.
FIG. 3 is a schematic structural view of a side section of a proton exchange membrane element in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
Referring to fig. 1 to 3, the organic wastewater treatment apparatus using a proton exchange membrane as a carrier according to the present invention includes:
the device comprises a reaction generator 1, wherein a water inlet 101 is formed in the lower part of the reaction generator 1, a water outlet 102 is formed in the upper part of the reaction generator 1, 5 proton exchange membrane elements 2 are arranged on the inner wall of the reaction generator 1 at intervals from the water inlet 101 to the water outlet 102, the proton exchange membrane elements 2 are of a hollow structure, and the hollow structure is communicated with the outside of the reaction generator; a flow regulating valve is arranged at the water inlet 101 of the reaction generator; a COD concentration detection probe 3 is arranged in the reaction generator 1 corresponding to the flow channel 103 on one side of each proton exchange membrane element 2, and the COD concentration detection probe 3 is electrically connected with a controller 5;
the side wall of the proton exchange membrane element 2 comprises from outside to inside in sequence: an anode gas diffusion and current collection layer 21, an anode catalyst layer 22, a proton exchange membrane 23, a cathode catalyst layer 24, a cathode gas diffusion and current collection layer 25;
the proton exchange membrane element 2 is connected with a direct current power supply 4, and the direct current power supply 4 is electrically connected with the controller 5.
Example 1
The organic wastewater treatment method comprises the following steps:
1) determining the range of operating voltage required for the electrolysis of organic waste water
Taking a certain amount of organic wastewater of a certain printing and dyeing mill, wherein the main component of the organic wastewater is methylene blue, detecting that the COD concentration in the organic wastewater is 1500ppm, dividing the organic wastewater into 15 parts with the same amount, electrolyzing each part of organic wastewater by using the proton exchange membrane element respectively, wherein the working voltage of the proton exchange membrane element corresponding to each part of organic wastewater is respectively 10V, 13V and … …, and the difference is sequentially increased gradually by 3V; after each part of organic wastewater is treated for 0.5h, measuring the COD concentration in each part of organic wastewater, and calculating the degradation rate of the organic matters and the acceleration rate of the degradation rate of the organic matters according to the measurement result, which is specifically shown in Table 1.
TABLE 1
From table 2, it is found that the working voltages of the proton exchange membrane elements corresponding to the maximum increase in the degradation rate of the organic matter in the organic wastewater are 28V and 31V, respectively, and it is determined that the working voltage range required for electrolyzing the organic wastewater is 25.2V to 34.1V.
2) Treatment of waste water
Setting the working voltage of a proton exchange membrane element 2 in the reaction generator 1 to be 30V; the organic wastewater to be treated flows in from the water inlet 101 of the reaction generator 1, the flow rate of the organic wastewater is controlled to be 1.1L/s by using a flow regulating valve, the organic wastewater sequentially contacts with the electrified proton exchange membrane element 2 to react and flows out from the water outlet 102 of the reaction generator 1, and the COD concentration in the organic wastewater flowing out from the water outlet 102 of the reaction generator 1 is 10ppm and meets the discharge standard.
Example 2
In this embodiment, the water outlet of the reaction generator is provided with a COD concentration detection probe, only one proton exchange membrane element is installed from the water inlet to the water outlet on the inner wall of the reaction generator, and the water outlet and the water inlet of the reaction generator are communicated through a pipeline with a circulation pump.
The organic waste water is organic waste water of a certain printing and dyeing mill, the main component of the organic waste water is methylene blue, the organic waste water enters from a water inlet of the reaction generator and flows out from a water outlet, and then the organic waste water returns to the reaction generator again through a pipeline with a circulating pump.
The initial COD concentration in the organic waste water and the COD concentration in the organic waste water after a period of treatment are respectively measured, the degradation rate of organic matters in the organic waste water in different time periods is respectively calculated according to the measurement result, and the specific result is shown in table 2:
TABLE 2
As can be seen from table 2:
a) under the same voltage, the higher the COD concentration in the organic wastewater is, the higher the degradation rate of the organic matters in the organic wastewater is;
b) on the premise of ensuring that the degradation rate of organic matters in the organic wastewater is similar, the lower the COD concentration of the organic wastewater is, the lower the required voltage is.
Therefore, in the organic wastewater treatment process, when the COD concentration in the organic wastewater is reduced, on the premise of ensuring that the degradation rate of organic matters in the organic wastewater is close, the power supply voltage of the proton exchange membrane element can be reduced in proportion, and the high-efficiency utilization of energy is realized.
Claims (10)
1. An organic wastewater treatment device taking a proton exchange membrane as a carrier is characterized by comprising:
the device comprises a reaction generator, a water inlet and a water outlet, wherein the lower part of the reaction generator is provided with the water inlet, the upper part of the reaction generator is provided with the water outlet, a plurality of proton exchange membrane elements are arranged on the inner wall of the reaction generator at intervals from the water inlet to the water outlet, the proton exchange membrane elements have hollow structures, and the hollow structures are communicated with the outside of the reaction generator;
the side wall of the proton exchange membrane element sequentially comprises from outside to inside: an anode gas diffusion and current collection layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer, a cathode gas diffusion and current collection layer;
the proton exchange membrane element is connected with a direct current power supply, and the direct current power supply is electrically connected with a controller.
2. The apparatus for treating organic wastewater with PEM as claimed in claim 1, wherein said reactor has several probes for detecting COD concentration on its inner wall, and said probes are electrically connected to said controller.
3. The apparatus of claim 1, wherein the proton exchange membrane elements are alternately arranged on the inner wall of the reaction generator to form zigzag channels.
4. The apparatus of claim 1, wherein a COD concentration detecting probe is installed in the reaction generator corresponding to the flow channel on one side of each proton exchange membrane element.
5. The apparatus for treating organic wastewater by using proton exchange membrane as carrier in claim 1, wherein the water inlet or outlet of the reaction generator is provided with a flow regulating valve.
6. The apparatus for treating organic wastewater by using proton exchange membrane as carrier according to claim 1 or 3, wherein the proton exchange membrane element is flat.
7. The device for treating organic wastewater by taking a proton exchange membrane as a carrier according to claim 1, wherein the anode gas diffusion and current collection layer is one or more layers of titanium meshes or titanium grids; the anode catalyst layer and the cathode catalyst layer are Pt/C electro-catalysts; the proton exchange membrane is a perfluorinated sulfonic acid polymer proton exchange membrane; the cathode gas diffusion and current collection layer is made of titanium, graphite or stainless steel.
8. The organic wastewater treatment method of the organic wastewater treatment device with the proton exchange membrane as the carrier based on any one of claims 1 to 7, which comprises the following steps:
1) determining the working voltage range required for electrolyzing the organic wastewater to be treated
Taking a certain amount of organic wastewater to be treated, measuring the concentration of organic matters of the organic wastewater, dividing the organic wastewater into N parts with the same quantity, putting the N parts into a reaction generator of an organic wastewater treatment device, electrolyzing each part of organic wastewater by a proton exchange membrane element respectively, wherein K is more than or equal to 1 and less than or equal to N, the working voltage of the proton exchange membrane element corresponding to each part of organic wastewater M (K) is U (K), sequentially increasing the working voltage of the proton exchange membrane element from U (1) to U (K), measuring the concentration of the organic matters in each part of organic wastewater after treating for the same time, calculating the degradation rate S (K) of the organic matters in each part of organic wastewater M (K) by dividing the treatment time by the concentration difference of the organic matters before and after each part of organic wastewater is treated, and then calculating the degradation rate acceleration of the:
wherein:
Δ (k): the degradation rate of organic matters in the kth to the kth plus 1 part of organic wastewater is increased, and the unit is ppm/hV;
s (k + 1): the degradation rate of organic matters in the k +1 part of organic wastewater is unit ppm/h;
s (k): the degradation rate of organic matters in the kth part of organic wastewater is unit ppm/h;
u (k + 1): working voltage of a proton exchange membrane element corresponding to the (k +1) th organic wastewater is unit V;
u (k): working voltage of a proton exchange membrane element corresponding to kth organic wastewater is unit V;
when the organic matter degradation rate is accelerated to the maximum, the corresponding working voltages of the proton exchange membrane elements are respectively U (k) and U (k +1), and then the working voltage range required by electrolyzing the organic wastewater to be treated is determined to be 90% U (k) to 110% U (k + 1);
2) treatment of waste water
Setting the working voltage of the proton exchange membrane element in the reaction generator within the working voltage range required for electrolyzing the organic wastewater to be treated determined in the step 1); the organic wastewater to be treated flows in from the water inlet of the reaction generator, is contacted with the electrified proton exchange membrane element in sequence to react, and flows out from the water outlet of the reaction generator.
9. The organic wastewater treatment method based on the proton exchange membrane supported organic wastewater treatment device as claimed in claim 8, wherein the operating voltage of the proton exchange membrane element in the step 2) is reduced along with the reduction of the concentration of the organic matters in the organic wastewater in the reaction generator during the organic wastewater treatment process.
10. The organic wastewater treatment method based on the proton exchange membrane-supported organic wastewater treatment device according to claim 8, wherein the organic wastewater needs to be pretreated before entering the reaction generator, and the pretreatment is one or more of acid-base regulation, coagulation, precipitation, adsorption and filtration.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748418A (en) * | 2008-12-11 | 2010-06-23 | 薛廷芳 | Bipolar membrane dual-liquid flow type hydroxyl radical generator |
| CN103806014A (en) * | 2014-01-24 | 2014-05-21 | 北京科技大学 | Proton exchange membrane water electrolysis device |
| CN106006860A (en) * | 2016-07-22 | 2016-10-12 | 北京航空航天大学 | High-salinity organic wastewater treatment device powered by solar energy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748418A (en) * | 2008-12-11 | 2010-06-23 | 薛廷芳 | Bipolar membrane dual-liquid flow type hydroxyl radical generator |
| CN103806014A (en) * | 2014-01-24 | 2014-05-21 | 北京科技大学 | Proton exchange membrane water electrolysis device |
| CN106006860A (en) * | 2016-07-22 | 2016-10-12 | 北京航空航天大学 | High-salinity organic wastewater treatment device powered by solar energy |
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