Intelligent wastewater treatment system combining ozone and micro-nano bubbles

Abstract

The present invention discloses an intelligent wastewater treatment system combining ozone and micro-nano bubbles, which comprises: an ozone preparation and supply device, which provides ozone; a micro-nano bubble generator, which is connected to the ozone preparation and supply device, a wastewater treatment device and an intelligent ozone dosing control model, which controls the amount of ozone provided by the ozone preparation and supply device to the micro-nano bubble generator according to the heavy metal ion content, COD content and working parameters of the micro-nano bubble generator in the wastewater. The present invention combines ozone with micro-nano bubbles to improve the solubility of ozone in water and the oxidation effect of ozone, promote the yield of hydroxyl radicals, and can play a synergistic enhancement effect on the removal effect of COD and heavy metal ions. The cavitation effect of the ultrasonic wave generated by the ultrasonic device disperses the pollution in the wastewater, which can strengthen the lateral migration of the micro-nano bubbles, further improve the mass transfer efficiency and reaction efficiency, and improve the wastewater treatment effect.

Description

Technical Field

[0001] The invention relates to the field of wastewater treatment, and in particular to an intelligent wastewater treatment system combining ozone and micro-nano bubbles. Background Art

[0002] Electroplating wastewater usually has a high COD and contains a large amount of heavy metal ions, such as chromium, nickel, copper, zinc, etc., as well as other toxic substances such as cyanide, etc., and the acid and alkali chemicals used in the electroplating process will cause the pH value of the wastewater to fluctuate greatly. Conventional treatment methods for electroplating wastewater, such as biodegradation, coagulation, adsorption, membrane separation and other physical and biological methods, usually make it difficult for the effluent to meet the water quality standards.

[0003] As a type of advanced oxidation technology, ozone technology has strong oxidation ability and can effectively remove organic matter, odor, color, heavy metals and other pollutants in water without residual or secondary pollution. In addition to directly reacting and oxidizing organic matter, ozone molecules can also decompose to produce highly active hydroxyl radicals to degrade organic matter. Micro-nano bubbles can promote the production of hydroxyl radicals in water due to their extremely small size and large specific surface area. Compared with traditional bubbling diffusion contactor aeration ozone technology, ozone micro-nano bubbles have a longer and more stable suspension time in water, higher mass transfer efficiency, higher gas-liquid interface area, and can provide more oxidation surfaces, thereby accelerating the oxidation reaction rate.

[0004] Combining ozone with micro-nano bubbles for the treatment of wastewater containing heavy metals and COD will have good application prospects, but there is currently a lack of reliable solutions. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide an intelligent wastewater treatment system combining ozone and micro-nano bubbles in view of the deficiencies in the above-mentioned prior art.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: an intelligent wastewater treatment system combining ozone and micro-nano bubbles, comprising:

[0007] An ozone preparation and supply device, which provides ozone;

[0008] A micro-nano bubble generator is connected to the ozone preparation and supply device.

[0009] A wastewater treatment device, wherein the wastewater to be treated is contained therein, and the wastewater treatment device is connected to a micro-nano water supply pipeline for conveying part of the wastewater inside the wastewater treatment device to the micro-nano bubble generator as water supply for the micro-nano bubble generator, and the micro-nano bubble generator conveys the micro-nano bubbles generated inside and the gas from the ozone preparation and supply device to the wastewater treatment device;

[0010] and an intelligent ozone dosing control model, which controls the amount of ozone provided by the ozone preparation and supply device to the micro-nano bubble generator according to the heavy metal ion content, COD content and the working parameters of the micro-nano bubble generator in the wastewater;

[0011] The working parameters of the micro-nano bubble generator include power, water intake and air intake of the micro-nano bubble generator.

[0012] Preferably, the intelligent ozone dosing control model includes:

[0013] Heavy metal ion calculation sub-model U1, which calculates the heavy metal ion concentration in the wastewater according to the conductivity of the wastewater;

[0014] The ozone dosage calculation sub-model U2 for removing heavy metal ions calculates the ozone dosage Q required to remove heavy metal ions in wastewater according to the heavy metal ion content in wastewater. M-O3 ;

[0015] The ozone dosage calculation sub-model U3 for removing COD is calculated based on the COD content in the wastewater and the working parameters of the micro-nano bubble generator to obtain the ozone dosage Q required to remove COD in the wastewater after deducting the effect of the micro-nano bubble generator. COD-O3 ;

[0016] Total ozone dosage calculation sub-model U4, which is used to calculate the total ozone dosage Q required to treat heavy metal ions and COD in wastewater O3 , Q O3 =Q M-O3 +Q COD-O3

[0017] and a control model, which controls the ozone preparation and supply device to provide a total amount of Q to the micro-nano bubble generator during the treatment process according to the calculation result of the total ozone dosage calculation sub-model U4. O3 of ozone.

[0018] Preferably, the heavy metal ion calculation sub-model U1 is represented by the following formula: M =k1×X σ +b1

[0019] Among them, CM is the heavy metal ion concentration, X σ is the conductivity of wastewater, k1 is the slope, k1 and b1 are known constants;

[0020] The construction method of the heavy metal ion measurement sub-model U1 is:

[0021] A series of heavy metal ion standard solutions with concentration gradients were prepared, and the conductivity of each heavy metal ion standard solution was measured. A linear fit was performed with the conductivity as the horizontal coordinate and the heavy metal ion concentration as the vertical coordinate. The obtained standard curve was the heavy metal ion measurement submodel U1.

[0022] Preferably, the ozone amount calculation sub-model U2 for removing heavy metal ions is expressed by the following formula: M-O3 =k2×X M +b2;

[0023] Among them, X M is the total amount of heavy metal ions in the wastewater, and the calculation formula is: X M =C M ×V0,C M , V0 are the heavy metal ion concentration in the wastewater and the total volume of the wastewater respectively, k2 is the slope, k2 and b2 are both known constants;

[0024] The construction method of the ozone amount measurement submodule U2 for removing heavy metal ions is as follows:

[0025] Prepare a series of heavy metal ion standard solutions with concentration gradients, add ozone to each heavy metal ion standard solution, record the amount of ozone added when the heavy metal ions are completely removed, and perform linear fitting with the heavy metal ion concentration as the horizontal axis and the ozone dosage as the vertical axis. The obtained standard curve is the sub-model U2 for measuring the amount of ozone required to remove heavy metal ions.

[0026] Preferably, the ozone amount measurement sub-model U3 for removing COD is expressed by the following formula:

[0027]

[0028] Among them, L COD is the total COD in the wastewater, and the calculation formula is: L COD =C0×V0, C0 and V0 are the COD concentration in the wastewater and the total volume of the wastewater respectively;

[0029] Among them, Q ·OH is the amount of ·OH produced by the micro-nano bubble generator during wastewater treatment, which is calculated by the pre-built ·OH calculation model U 30 Calculated;

[0030] Among them, q1 is the amount of COD that can be degraded by a unit amount of ozone, and q2 is the amount of COD that can be degraded by a unit amount of ·OH.

[0031] Preferably, the ·OH calculation model U 30 It is constructed by the following method:

[0032] S1. Build training set:

[0033] The micro-nano bubble generator was placed in deionized water, and the amount of OH produced Q· at different treatment times t under different working parameters G was recorded. OH ;

[0034] Note the working parameter G i Next, at time t i The amount of OH produced is Q i · OH , G i ,t i , Q i · OH Combined into a training data s i , combine all the obtained training data to obtain the training set S;

[0035] Among them, the working parameters G of the micro-nano bubble generator include power P, water inlet Q w , intake volume Q A ;

[0036] S2. Model training:

[0037] Based on the RNN recurrent neural network model, the working parameters of the micro-nano bubble generator: power P, water inlet Q w , intake volume Q A and processing time t as input, corresponding to the OH amount Q· in the training data OH Train for the expected output value, with L MSEloss is the loss function. After training, we get the OH estimation model U 30 , L MSEloss The formula is:

[0038] L MSEloss =A1×MSE+A2×RMSE+A3×MAE+A4×R2;

[0039]

[0040]

[0041] Among them, m is the number of training data, y i is the model prediction output, is the expected output value, is the average value of the model prediction output;

[0042] Among them, A1, A2, A3, and A4 are weighted coefficients, which are calculated by the following method:

[0043] S2-1. For each training data i, calculate its prediction error e i =|y i -y^ i ∣;

[0044] S2-2. Calculate the weighted coefficient w of training data i i , w i =1 / (e i +∈), where ∈ is a constant used to avoid the denominator being zero;

[0045] S2-3, standardize the weighting coefficients so that their sum is equal to the total number of training numbers, and then calculate the weighting coefficients A1, A2, A3, and A4 using the following formula:

[0046]

[0047]

[0048] Preferably, q1 is obtained by the following method:

[0049] Take concentration C b 、Volume V b COD standard solution, add ozone to it until the COD in it is completely degraded, and record the ozone dosage Q at this time b-O3 , and then calculate the amount of COD that can be degraded by a unit amount of ozone q1:

[0050]

[0051] q2 is obtained by:

[0052] 1) Take concentration C b 、Volume V b The COD standard solution is processed by the micro-nano bubble generator, and the power of the micro-nano bubble generator is controlled to P wb , water inflow is Q wb , the air intake volume is Q Ab , until the COD is completely degraded, and the treatment time t is recorded b ;

[0053] 2) The working parameters of the micro-nano bubble generator: power P wb , water inflow Q wb , intake volume Q Ab and processing time tb Input OH calculation model U 30 The output is the amount of OH produced by the micro-nano bubble generator Q b·OH ;

[0054] 3) Finally, calculate the amount of COD that can be degraded by a unit amount of OH, q2:

[0055]

[0056] Preferably, the ozone preparation and supply device comprises an air pump, an oxygen generator, an ozone generator and a pressure-stabilizing tank which are sequentially connected through a main gas pipeline, and the pressure-stabilizing tank is connected to the micro-nano bubble generator;

[0057] A first solenoid valve is provided between the air pump and the oxygen concentrator, a second solenoid valve is provided between the oxygen concentrator and the ozone generator, a third solenoid valve is provided between the ozone generator and the pressure-stabilizing tank, and a fourth solenoid valve is provided between the pressure-stabilizing tank and the micro-nano bubble generator;

[0058] The main gas supply pipeline between the air pump and the first solenoid valve is connected with an auxiliary gas supply pipeline, and the end of the auxiliary gas supply pipeline is connected to the micro-nano bubble generator;

[0059] The oxygen concentrator is connected to the auxiliary gas pipeline through a first branch pipe, and the ozone generator is connected to the auxiliary gas pipeline through a second branch pipe;

[0060] A fifth solenoid valve is arranged on the secondary air supply pipeline between the air pump and the first branch pipe, a sixth solenoid valve is arranged on the first branch pipe, and a seventh solenoid valve is arranged on the second branch pipe.

[0061] Preferably, the wastewater treatment device comprises a conical treatment tank, an upper opening opened at the top of the treatment tank, a plurality of ultrasonic devices arranged on the inner wall of the treatment tank, an aeration device arranged in the middle of the treatment tank, a gas treatment device arranged at the upper opening, a water outlet pipe arranged above the side of the treatment tank, a water inlet pipe arranged below the side of the treatment tank, and a mud discharge pipe arranged at the bottom of the treatment tank;

[0062] The mud discharge pipe is provided with a mud discharge valve;

[0063] The aeration device includes an air intake main pipe inserted into the treatment tank through an upper opening and a plurality of air intake branch pipe units connected to the air intake main pipe at uniform intervals in a vertical direction. The air intake branch pipe units include a plurality of air intake branch pipes annularly connected to the air intake main pipe, and a plurality of air intake holes are opened on the air intake branch pipes.

[0064] Preferably, a filter membrane assembly is provided on the water outlet pipe, a clean water drainage pipe and a concentrated water return pipe are connected to the filter membrane assembly, and the end of the concentrated water return pipe is connected to the water inlet pipe;

[0065] The ultrasonic device comprises an ultrasonic generator and an ultrasonic transducer connected to the ultrasonic generator, and the ultrasonic transducer is located between the water inlet pipe and the water outlet pipe in the vertical direction.

[0066] Preferably, the micro-nano water supply pipeline is provided with a dosing device and a water diversion pump.

[0067] Preferably, the system further comprises a monitoring device, which is arranged on the wastewater treatment device and is used at least to monitor the conductivity and COD concentration of the wastewater.

[0068] The beneficial effects of the present invention are:

[0069] (1) The present invention combines ozone with micro-nano bubbles to improve the solubility of ozone in water and the oxidation effect of ozone, promote the yield of hydroxyl radicals, and achieve a synergistic enhancement effect on the removal of COD and heavy metal ions;

[0070] (2) The bubbles generated by the micro-nano bubble generator have the characteristics of small particle size and large specific surface area, which are helpful to remove sediments and dirt on the membrane surface of the membrane assembly; the ozone micro-nano bubbles have higher dissolved oxygen mass transfer efficiency, which can greatly improve the gas-liquid mass transfer rate and concentration peak of ozone in the water body, and can effectively prolong the residence time of ozone in water. At the same time, it can produce ozone bubble water by combining with ozone. The rupture of ozone bubbles can produce a large number of hydroxyl free radicals, which can effectively enhance the oxidation ability of ozone and strengthen the removal effect of ozone on difficult-to-degrade organic pollutants;

[0071] (3) The ozone preparation and supply device of the present invention can achieve a stable supply of ozone, and by controlling the solenoid valves, air pumps, oxygen generators, and ozone generators in the ozone preparation and supply device, gas media with different components (air, oxygen, ozone, or a mixture thereof) can be provided to the micro-nano bubble generator, thereby broadening the application scenarios.

[0072] (4) The cavitation effect of ultrasonic waves generated by the ultrasonic device disperses the pollution in the wastewater, which can enhance the lateral migration of micro-nano bubbles, further improve the mass transfer efficiency and reaction efficiency, and improve the wastewater treatment effect;

[0073] (5) The system of the present invention can calculate the amount of ozone required based on the heavy metal ions and COD in the wastewater, and can deduct the amount of COD that can be degraded by the hydroxyl radicals OH generated when the micro-nano bubbles burst, thereby greatly reducing the amount of ozone used, improving the ozone utilization efficiency, and reducing the cost of wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is a schematic diagram of the overall structure of the wastewater intelligent treatment system combining ozone and micro-nano bubbles of the present invention;

[0075] Figure 2 It is a schematic diagram of the structure of the ozone preparation and supply device and the micro-nano bubble generator of the present invention;

[0076] Figure 3 It is a structural schematic diagram of the wastewater treatment device of the present invention;

[0077] Figure 4 It is a schematic diagram of the principle structure of the intelligent ozone dosing control model of the present invention;

[0078] Figure 5 The OH calculation model U of the present invention is 30 Schematic diagram of the construction process;

[0079] Figure 6 It is a schematic diagram of the calculation process of the weighted coefficient of the present invention;

[0080] Figure 7 It is a schematic diagram of the calculation process of q2 of the present invention;

[0081] Figure 8 COD and Cu in the test example of the present invention 2+ The removal result.

[0082] Description of reference numerals:

[0083] 1—Ozone preparation and supply device; 10—Main gas pipeline; 11—Air pump; 12—Oxygen generator; 13—Ozone generator; 14—Pressure regulator tank; 15—Auxiliary gas pipeline; 16—First branch pipe; 17—Second branch pipe;

[0084] 2—Micro-nano bubble generator;

[0085] 3—wastewater treatment device; 30—micro-nano water supply pipeline; 31—treatment tank; 32—upper opening; 33—ultrasonic device; 34—aeration device; 35—gas treatment device; 36—water outlet pipe; 37—water inlet pipe; 38—mud discharge pipe; 39—micro-nano water supply port;

[0086] 300—dosing device; 301—water pump; 330—ultrasonic generator; 331—ultrasonic transducer; 340—air intake main pipe; 341—air intake branch pipe unit; 380—mud discharge valve;

[0087] 4—Intelligent ozone dosing control model;

[0088] 5—filter membrane assembly; 50—clean water drainage pipe; 51—concentrated water return pipe;

[0089] 6—Monitoring device;

[0090] 70—first solenoid valve; 71—second solenoid valve; 72—third solenoid valve; 73—fourth solenoid valve; 74—fifth solenoid valve; 75—sixth solenoid valve; 76—seventh solenoid valve. DETAILED DESCRIPTION

[0091] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0092] It should be understood that terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0093] Example 1

[0094] Reference Figure 1-3 This embodiment provides an intelligent wastewater treatment system combining ozone and micro-nano bubbles, including:

[0095] An ozone preparation and supply device 1, which provides ozone;

[0096] The micro-nano bubble generator 2 is connected to the ozone preparation and supply device 1.

[0097] The wastewater treatment device 3 contains wastewater to be treated. The wastewater treatment device 3 is connected to a micro-nano water supply pipeline 30 for conveying part of the wastewater inside the wastewater treatment device 3 to the micro-nano bubble generator 2 as water supply for the micro-nano bubble generator 2. The micro-nano bubble generator 2 conveys the micro-nano bubbles generated inside and the gas from the ozone preparation and supply device 1 to the wastewater treatment device 3.

[0098] and an intelligent ozone dosing control model 4, which controls the amount of ozone provided by the ozone preparation and supply device 1 to the micro-nano bubble generator 2 according to the heavy metal ion content, COD content and working parameters of the micro-nano bubble generator 2 in the wastewater;

[0099] The working parameters of the micro-nano bubble generator 2 include the power, water intake and air intake of the micro-nano bubble generator 2 .

[0100] In this embodiment, the ozone preparation and supply device 1 includes an air pump 11, an oxygen generator 12, an ozone generator 13 and a pressure-suppressing tank 14 which are sequentially connected through a main gas pipeline 10, and the pressure-suppressing tank 14 is connected to the micro-nano bubble generator 2;

[0101] A first solenoid valve 70 is provided between the air pump 11 and the oxygen generator 12, a second solenoid valve 71 is provided between the oxygen generator 12 and the ozone generator 13, a third solenoid valve 72 is provided between the ozone generator 13 and the pressure-suppressing tank 14, and a fourth solenoid valve 73 is provided between the pressure-suppressing tank 14 and the micro-nano bubble generator 2;

[0102] The main gas pipeline 10 between the air pump 11 and the first solenoid valve 70 is connected with an auxiliary gas pipeline 15, and the end of the auxiliary gas pipeline 15 is connected to the micro-nano bubble generator 2;

[0103] The oxygen generator 12 is connected to the auxiliary gas pipeline 15 through the first branch pipe 16, and the ozone generator 13 is connected to the auxiliary gas pipeline 15 through the second branch pipe 17;

[0104] A fifth solenoid valve 74 is provided on the secondary air supply pipeline 15 between the air pump 11 and the first branch pipe 16 , a sixth solenoid valve 75 is provided on the first branch pipe 16 , and a seventh solenoid valve 76 is provided on the second branch pipe 17 .

[0105] The ozone preparation and supply device 1 is mainly used to provide ozone to the micro-nano bubble generator 2, but is not limited thereto. In this embodiment, through the control of the first to seventh solenoid valves 76, oxygen or air or a mixture of two or three of ozone, oxygen and air in any proportion can also be provided, thereby improving its adaptability to wastewater quality and expanding its application scenarios. The specific principle is:

[0106] When the first solenoid valve 70, the second solenoid valve 71, and the third solenoid valve 72 are opened, and the other solenoid valves are closed, and the air pump 11, the oxygen generator 12, and the ozone generator 13 are all working, pure ozone is provided to the micro-nano bubble generator 2;

[0107] When the fifth solenoid valve 74 is opened, the other solenoid valves are closed, and only the air pump 11 is working, pure air is provided to the micro-nano bubble generator 2;

[0108] When the first solenoid valve 70 and the fifth solenoid valve 74 are opened, the air pump 11 and the oxygen generator 12 are both working, and pure oxygen is provided to the micro-nano bubble generator 2;

[0109] According to the above principle, by controlling each solenoid valve and the air pump 11, the oxygen generator 12, and the ozone generator 13, the composition of the gas medium provided to the micro-nano bubble generator 2 can be adjusted, thereby broadening the application scenarios.

[0110] In this embodiment, the wastewater treatment device 3 includes a conical treatment tank 31, an upper opening 32 opened at the top of the treatment tank 31, a plurality of ultrasonic devices 33 arranged on the inner wall of the treatment tank 31, an aeration device 34 arranged in the middle of the treatment tank 31, a gas treatment device 35 arranged at the upper opening 32 (used to treat ozone escaped during the reaction, methane produced by oxidation and other possible toxic gases to avoid environmental pollution), a water outlet pipe 36 arranged above the side of the treatment tank 31, a water inlet pipe 37 arranged below the side of the treatment tank 31, and a mud discharge pipe 38 arranged at the bottom of the treatment tank 31;

[0111] The mud discharge pipe 38 is provided with a mud discharge valve 380. When the heavy metal sludge accumulates to a certain amount, the mud discharge valve 380 opens to discharge the heavy metal sludge for recovery.

[0112] The aeration device 34 includes an air intake main pipe 340 inserted into the treatment tank 31 through the upper opening 32 and a plurality of air intake branch pipe units 341 connected to the air intake main pipe 340 at uniform intervals in the vertical direction. The air intake branch pipe units 341 include a plurality of air intake branch pipes connected to the air intake main pipe 340 in an annular manner. The air intake branch pipes are provided with a plurality of air intake holes. The aeration device 34 forms an annular, multi-layer aeration, which is conducive to achieving uniform distribution of ozone micro-nano bubbles.

[0113] Ozone has a strong oxidizing ability and can effectively remove various pollutants such as organic matter, odor, color, heavy metals, etc. in water. In addition to directly reacting to oxidize and degrade organic matter, ozone molecules can also decompose to produce highly active hydroxyl radicals to degrade organic matter. Micro-nano bubbles have extremely small size, high surface energy and strong gasification effect, which are helpful to remove sediments and dirt on the membrane surface of the membrane assembly. The present invention combines ozone with micro-nano bubbles to improve the solubility of ozone in water and the oxidizing effect of ozone, and promotes the yield of hydroxyl radicals.

[0114] The ultrasonic device 33 includes an ultrasonic generator 330 and an ultrasonic transducer 331 connected to the ultrasonic generator 330. The ultrasonic transducer 331 is located between the water inlet pipe 37 and the water outlet pipe 36 in the vertical direction. The ultrasonic generator 330 emits ultrasonic vibrations into the treatment tank 31 in a counter-radiation manner, and the ultrasonic transducer 331 receives the power signal emitted by the ultrasonic generator 330 and converts it into mechanical vibration. The cavitation effect of the ultrasonic wave can disperse the pollutants in the wastewater, increase the solubility of ozone in water and the oxidation effect of ozone, promote the yield of hydroxyl radicals, and enhance the removal of difficult-to-degrade pollutants.

[0115] A filter membrane assembly 5 is provided on the water outlet pipe 36, and a clean water drain pipe 50 and a concentrated water return pipe 51 are connected to the filter membrane assembly 5. The end of the concentrated water return pipe 51 is connected to the water inlet pipe 37. A filter membrane is provided in the filter membrane assembly 5. Water passing through the filter membrane enters the clean water drain pipe 50, and is discharged as qualified water after being tested. The water retained by the filter membrane enters the concentrated water return pipe 51 as concentrated water, and then flows back to the treatment tank 31 for further purification.

[0116] A micro-nano water supply port 39 is provided on the side of the treatment tank 31, and the nano water supply pipeline is connected to the micro-nano water supply port 39, so that part of the wastewater is circulated and transported to the micro-nano bubble generator 2 as its water source, thereby eliminating the need for additional water supply. In a preferred embodiment, a dosing device 300 and a water diversion pump 301 are provided on the micro-nano water supply pipeline 30. pH regulators, flocculants, coagulants, catalysts, etc. can be added through the dosing device 300 to assist in wastewater treatment, and the specific selection is made according to actual conditions.

[0117] The system also includes a monitoring device 6, which is arranged on the wastewater treatment device 3 and is used to monitor at least the conductivity and COD concentration of the wastewater. The monitoring device 6 is used to monitor the quality of the wastewater, wherein the COD concentration is indirectly measured by measuring the redox potential using a glassy carbon electrode, and the conductivity is measured by a conductivity detector.

[0118] Ozone is the main active substance for removing heavy metal ions and COD. Its dosage is determined according to the amount of heavy metal ions and COD in the wastewater, which can ensure that the treatment requirements are met and the amount of ozone used is reduced as much as possible. Among them, the combination of ozone and the micro-nano bubble generator 2 can have a synergistic enhancement effect on the removal effect of COD. One of the reasons is that when the micro-nano bubbles burst, hydroxyl radicals ·OH will be generated. The ·OH radicals will indirectly participate in the degradation of organic matter. Therefore, if the amount of COD that can be degraded by the micro-nano bubble generator 2 can be calculated, the amount of ozone required to degrade this part of COD can be deducted when calculating the total dosage of ozone, thereby reducing the amount of ozone used and reducing the treatment cost.

[0119] In this embodiment, the above purpose can be achieved by using an energy-based ozone dosing control model. For details, refer to Figure 4 , Intelligent ozone dosing control model 4 includes:

[0120] Heavy metal ion calculation sub-model U1, which calculates the heavy metal ion concentration in the wastewater according to the conductivity of the wastewater;

[0121] The ozone dosage calculation sub-model U2 for removing heavy metal ions calculates the ozone dosage Q required to remove heavy metal ions in wastewater according to the heavy metal ion content in wastewater. M-O3 ;

[0122] The ozone dosage calculation sub-model U3 for removing COD is used to calculate the ozone dosage Q required for removing COD in the wastewater after deducting the effect of the micro-nano bubble generator 2 according to the COD content in the wastewater and the working parameters of the micro-nano bubble generator 2. COD-O3 ;

[0123] Total ozone dosage calculation sub-model U4, which is used to calculate the total ozone dosage Q required to treat heavy metal ions and COD in wastewater O3 , Q O3 =Q M-O3 +Q COD-O3

[0124] And a control model, which controls the ozone preparation and supply device 1 to provide a total amount of Q to the micro-nano bubble generator 2 during the treatment process according to the calculation result of the total ozone dosage calculation sub-model U4 O3 of ozone.

[0125] In this embodiment, the heavy metal ion measurement sub-model U1 is expressed by the following formula: M =k1×X σ +b1

[0126] Among them, C M is the heavy metal ion concentration, X σ is the conductivity of wastewater, k1 is the slope, k1 and b1 are known constants;

[0127] The construction method of the heavy metal ion measurement sub-model U1 is:

[0128] Prepare a series of heavy metal ion standard solutions with concentration gradients, measure the conductivity of each heavy metal ion standard solution (determined by a conductivity detector), and perform linear fitting with conductivity as the horizontal axis and heavy metal ion concentration as the vertical axis. The obtained standard curve is the heavy metal ion measurement submodel U1.

[0129] Furthermore, the ozone amount measurement sub-model U2 for removing heavy metal ions is expressed by the following formula: Q M-O3 =k2×X M +b2;

[0130] Among them, X M is the total amount of heavy metal ions in the wastewater, and the calculation formula is: X M =C M ×V0,C M , V0 are the heavy metal ion concentration in the wastewater and the total volume of the wastewater respectively, k2 is the slope, k2 and b2 are known constants;

[0131] The construction method of the calculation submodule U2 for measuring the amount of ozone required for removing heavy metal ions is as follows:

[0132] A series of heavy metal ion standard solutions with concentration gradients were prepared, ozone was added to each heavy metal ion standard solution, and the amount of ozone added when the heavy metal ions were completely removed (the concentration was considered to be completely removed when it reached a set threshold) was recorded. A linear fit was performed with the heavy metal ion concentration as the horizontal axis and the ozone dosage as the vertical axis. The obtained standard curve was the sub-model U2 for measuring the amount of ozone required to remove heavy metal ions.

[0133] In this embodiment, the ozone amount measurement sub-model U3 for removing COD is expressed by the following formula:

[0134]

[0135] Among them, L COD is the total COD in the wastewater, and the calculation formula is: L COD =C0×V0, C0 and V0 are the COD concentration in the wastewater and the total volume of the wastewater respectively;

[0136] Among them, Q ·OH is the amount of ·OH produced by the micro-nano bubble generator 2 during wastewater treatment, which is calculated by the pre-built ·OH calculation model U 30 Calculated;

[0137] Among them, q1 is the amount of COD that can be degraded by a unit amount of ozone, and q2 is the amount of COD that can be degraded by a unit amount of ·OH.

[0138] Reference Figure 5 In this embodiment, the OH calculation model U 30 It is constructed by the following method:

[0139] S1. Build training set:

[0140] Place the micro-nano bubble generator 2 in deionized water and record the amount of OH produced at different treatment times t under different working parameters G. OH ;

[0141] Note the working parameter G i Next, at time t i The amount of OH produced is Q i · OH , G i ,t i , Q i · OH Combined into a training data s i , combine all the obtained training data to obtain the training set S;

[0142] Among them, the working parameters G of the micro-nano bubble generator 2 include power P, water inlet Q w , intake volume QA ;

[0143] S2. Model training:

[0144] Based on the RNN recurrent neural network model, the working parameters of the micro-nano bubble generator 2: power P, water inlet Q w , intake volume Q A and processing time t as input, corresponding to the OH amount Q· in the training data OH Train for the expected output value, with L MSEloss is the loss function. After training, we get the OH estimation model U 30 , L MSEloss The formula is:

[0145] L MSEloss =A1×MSE+A2×RMSE+A3×MAE+A4×R2;

[0146]

[0147]

[0148] MSE is the mean square error (Mean Square Error): range [0, +∞), when the predicted value is completely consistent with the true value, it is equal to 0, that is, a perfect model. RMSE is the root mean square error (Root Mean Square Error): range [0, +∞), when the predicted value is completely consistent with the true value, it is equal to 0, that is, a perfect model. MAE is the mean absolute error (Mean Absolute Error): range [0, +∞), when the predicted value is completely consistent with the true value, it is equal to 0, that is, a perfect model. R2 is the coefficient of determination (R-Square): the value range is [0, 1]. The closer the value is to 1, the better the model fitting effect.

[0149] Among them, m is the number of training data, y i is the model prediction output, is the expected output value, is the average value of the model prediction output;

[0150] Among them, A1, A2, A3, A4 are weighted coefficients, refer to Figure 6 , calculated by the following method:

[0151] S2-1. For each training data i, calculate its prediction error e i =|y i -y^ i ∣;

[0152] S2-2. Calculate the weighted coefficient w of training data i i, w i =1 / (e i +∈), where ∈ is a constant used to avoid the denominator being zero;

[0153] S2-3, standardize the weighting coefficients so that their sum is equal to the total number of training numbers, and then calculate the weighting coefficients A1, A2, A3, and A4 using the following formula:

[0154]

[0155]

[0156] In this embodiment, q1 is obtained by the following method:

[0157] Take concentration C b 、Volume V b COD standard solution is added with ozone until the COD (COD concentration is indirectly determined by measuring the redox potential using a glassy carbon electrode) is completely degraded (concentration is considered to be completely reduced when it reaches the set threshold), and the ozone dosage Q is recorded at this time. b-O3 , and then calculate the amount of COD that can be degraded by a unit amount of ozone q1:

[0158]

[0159] Reference Figure 7 , q2 is obtained by:

[0160] (1) Take the concentration C b 、Volume V b The COD standard solution is processed by the micro-nano bubble generator 2, and the power of the micro-nano bubble generator 2 is controlled to be P wb , water inflow is Q wb , the air intake volume is Q Ab , until the COD is completely degraded, and the treatment time t is recorded b ;

[0161] (2) The working parameters of the micro-nano bubble generator 2: power P wb , water inflow Q wb , intake volume Q Ab and processing time t b Input OH calculation model U 30 The output is the amount of OH produced by the micro-nano bubble generator 2, Q b·OH ;

[0162] (3) Finally, calculate the amount of COD that can be degraded by a unit amount of OH:

[0163]

[0164] Example 2

[0165] An intelligent wastewater treatment process combining ozone and micro-nano bubbles, which uses the system of Example 1 to treat wastewater, and the specific steps include:

[0166] (1) Inputting wastewater to be treated into the treatment tank 31, obtaining the volume of the wastewater, and obtaining the heavy metal ion concentration and COD concentration in the wastewater through the monitoring device 6;

[0167] (2) Setting the working parameter G of the micro-nano bubble generator 2 and the wastewater treatment time t; the intelligent ozone dosing control model 4 obtains the following data: the volume of wastewater, the working parameter G of the micro-nano bubble generator 2 and the wastewater treatment time, and analyzes and obtains the required total ozone dosage Q O3 , and control the ozone preparation and supply device 1 so that the ozone preparation and supply device 1 provides a total amount of Q to the micro-nano bubble generator 2 within a time t O3 ozone (the first solenoid valve 70, the second solenoid valve 71, and the third solenoid valve 72 are opened, the other solenoid valves are closed, and the air pump 11, the oxygen generator 12, and the ozone generator 13 are all working);

[0168] During the treatment process, the reagent is added through the dosing device 300 according to actual needs;

[0169] During the treatment process, the ultrasonic device 33 works simultaneously;

[0170] (3) After the treatment is completed, the heavy metal ion concentration and COD concentration of the wastewater in the treatment tank 31 are detected by the monitoring device 6. When the preset requirements are met, the wastewater is discharged through the outlet pipe 36. The discharged water is filtered by the filter membrane assembly 5, and the clean water discharged from the clean water discharge pipe 50 is discharged as qualified water after being tested. If the monitoring device 6 detects that the heavy metal ion concentration and COD concentration of the wastewater in the treatment tank 31 do not meet the preset requirements, ozone is added manually and the treatment time is extended until the preset requirements are met, and the actual total ozone dosage Q' at this time can be recorded and saved. O3 and the actual wastewater treatment time t', which can be used as training data for the OH estimation model U in the later stage. 30 Make optimizations.

[0171] When the heavy metal sludge at the bottom of the treatment tank 31 accumulates to a certain amount, the sludge discharge valve 380 is opened to discharge the heavy metal sludge for recovery.

[0172] Test Case

[0173] The COD concentration was 190 mg / L and Cu 2+The concentration of the solution is 10mg / L, the water volume is 12L, and the working parameters G of the micro-nano bubble generator 2 are as follows: power P = 250W, water inlet Q w =200L / h, air intake volume Q A =500mlL / min; processing time t=40min;

[0174] The intelligent ozone dosing control model 4 analyzes that the amount of ozone to be added is 1200 mg, and then controls the ozone preparation and supply device 1 to evenly supply it to the micro-nano bubble generator 2 within 40 minutes;

[0175] During the treatment process, the COD concentration and Cu in the wastewater are detected by monitoring device 6. 2+ Concentration, processing results such as Figure 8 As shown in the figure, it can be seen that the system has a significant effect on COD and Cu 2+ The removal has a very good effect.

[0176] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. An intelligent wastewater treatment system combining ozone and micro-nano bubbles, characterized in that: include: An ozone preparation and supply device, which provides ozone; A micro-nano bubble generator is connected to the ozone preparation and supply device. A wastewater treatment device, wherein the wastewater to be treated is contained therein, and the wastewater treatment device is connected to a micro-nano water supply pipeline for conveying part of the wastewater inside the wastewater treatment device to the micro-nano bubble generator as water supply for the micro-nano bubble generator, and the micro-nano bubble generator conveys the micro-nano bubbles generated inside and the gas from the ozone preparation and supply device to the wastewater treatment device; and an intelligent ozone dosing control model, which controls the amount of ozone provided by the ozone preparation and supply device to the micro-nano bubble generator according to the heavy metal ion content, COD content and the working parameters of the micro-nano bubble generator in the wastewater; The working parameters of the micro-nano bubble generator include the power, water intake and air intake of the micro-nano bubble generator; The intelligent ozone dosing control model includes: Heavy metal ion calculation sub-model U1, which calculates the heavy metal ion concentration in the wastewater according to the conductivity of the wastewater; The ozone dosage calculation sub-model U2 for removing heavy metal ions calculates the ozone dosage Q required to remove heavy metal ions in wastewater according to the heavy metal ion content in wastewater. M-O3 ; The ozone dosage calculation sub-model U3 for removing COD is used to calculate the ozone dosage Q required to remove COD in the wastewater after deducting the effect of the micro-nano bubble generator based on the COD content in the wastewater and the working parameters of the micro-nano bubble generator. COD-O3 ; Total ozone dosage calculation sub-model U4, which is used to calculate the total ozone dosage Q required to treat heavy metal ions and COD in wastewater O3 , Q O3 =Q M-O3 +Q COD-O3 and a control model, which controls the ozone preparation and supply device to provide a total amount of Q to the micro-nano bubble generator during the treatment process according to the calculation result of the total ozone dosage calculation sub-model U4. O3 ozone; The ozone amount measurement sub-model U3 for removing COD is expressed by the following formula: ; Among them, L COD is the total COD in the wastewater, and the calculation formula is: L COD =C0×V0, C0 and V0 are the COD concentration in the wastewater and the total volume of the wastewater respectively; in, is the amount of ·OH produced by the micro-nano bubble generator during wastewater treatment, which is calculated by the pre-built ·OH calculation model U 30 Calculated; Among them, q1 is the amount of COD that can be degraded by a unit amount of ozone, and q2 is the amount of COD that can be degraded by a unit amount of ·OH; The construction method of the heavy metal ion measurement sub-model U1 is: Prepare a series of heavy metal ion standard solutions with concentration gradients, measure the conductivity of each heavy metal ion standard solution, and perform linear fitting with conductivity as the horizontal coordinate and heavy metal ion concentration as the vertical coordinate. The obtained standard curve is the heavy metal ion measurement sub-model U1; Among them, the ·OH calculation model U 30 It is constructed by the following method: S1. Build training set: The micro-nano bubble generator was placed in deionized water, and the amount of OH produced Q· at different treatment times t under different working parameters G was recorded. OH ; Note the working parameter G i Next, at time t i The amount of OH produced is Q i · OH , G i ,t i , Q i · OH Combined into a training data s i , combine all the obtained training data to obtain the training set S; Among them, the working parameters G of the micro-nano bubble generator include power P, water inlet Q w , intake volume Q A ; S2. Model training: Based on the RNN recurrent neural network model, the working parameters of the micro-nano bubble generator: power P, water inlet Q w , intake volume Q A and processing time t as input, corresponding to the OH amount Q· in the training data OH Train for the expected output value, with L MSEloss is the loss function. After training, we get the OH calculation model U 30 .

2. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 1 is characterized in that: The heavy metal ion calculation sub-model U1 is expressed by the following formula: M =k1×X σ +b1 Among them, C M is the heavy metal ion concentration, X σ is the conductivity of the wastewater, k1 is the slope, and k1 and b1 are known constants.

3. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 2 is characterized in that: The ozone amount calculation sub-model U2 for removing heavy metal ions is expressed by the following formula: M-O3 =k2×X M +b2; Among them, X M is the total amount of heavy metal ions in the wastewater, and the calculation formula is: X M =C M ×V0,C M , V0 are the heavy metal ion concentration in the wastewater and the total volume of the wastewater respectively, k2 is the slope, k2 and b2 are both known constants; The construction method of the ozone amount measurement submodule U2 for removing heavy metal ions is as follows: Prepare a series of heavy metal ion standard solutions with concentration gradients, add ozone to each heavy metal ion standard solution, record the amount of ozone added when the heavy metal ions are completely removed, and perform linear fitting with the heavy metal ion concentration as the horizontal axis and the ozone dosage as the vertical axis. The obtained standard curve is the sub-model U2 for measuring the amount of ozone required to remove heavy metal ions.

4. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 3 is characterized in that: L MSEloss The formula is: ； ； ； ； ； Among them, m is the number of training data, y i is the model prediction output, is the expected output value, is the average value of the model prediction output; Among them, A1, A2, A3, and A4 are weighted coefficients, which are calculated by the following method: S2-1. For each training data i, calculate its prediction error e i =|y i −y^ i ∣; S2-2. Calculate the weighted coefficient w of training data i i , w i =1 / (e i +ϵ), where ϵ is a constant used to avoid the denominator being zero; S2-3, standardize the weighting coefficients so that their sum is equal to the total number of training numbers, and then calculate the weighting coefficients A1, A2, A3, and A4 using the following formula: ； ； ； 。 5. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 4 is characterized in that: q1 is obtained by: Take concentration C b 、Volume V b COD standard solution, add ozone to it until the COD in it is completely degraded, and record the ozone dosage Q at this time b-O3 , and then calculate the amount of COD that can be degraded by a unit amount of ozone q1: ； q2 is obtained by: 1) Take concentration C b 、Volume V b The COD standard solution is processed by the micro-nano bubble generator, and the power of the micro-nano bubble generator is controlled to P wb , water inflow is Q wb , the air intake volume is Q Ab , until the COD is completely degraded, and the treatment time t is recorded b ; 2) The working parameters of the micro-nano bubble generator: power P wb , water inflow Q wb , intake volume Q Ab and processing time t b Input OH calculation model U 30 The output is the amount of OH produced by the micro-nano bubble generator Q b·OH ; 3) Finally, calculate the amount of COD that can be degraded by a unit amount of OH, q2: 。 6. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 1 is characterized in that: The ozone preparation and supply device comprises an air pump, an oxygen generator, an ozone generator and a pressure-stabilizing tank which are sequentially connected through a main gas pipeline, and the pressure-stabilizing tank is connected to the micro-nano bubble generator; A first solenoid valve is provided between the air pump and the oxygen concentrator, a second solenoid valve is provided between the oxygen concentrator and the ozone generator, a third solenoid valve is provided between the ozone generator and the pressure-stabilizing tank, and a fourth solenoid valve is provided between the pressure-stabilizing tank and the micro-nano bubble generator; The main gas supply pipeline between the air pump and the first solenoid valve is connected with an auxiliary gas supply pipeline, and the end of the auxiliary gas supply pipeline is connected to the micro-nano bubble generator; The oxygen concentrator is connected to the auxiliary gas pipeline through a first branch pipe, and the ozone generator is connected to the auxiliary gas pipeline through a second branch pipe; A fifth solenoid valve is arranged on the secondary air supply pipeline between the air pump and the first branch pipe, a sixth solenoid valve is arranged on the first branch pipe, and a seventh solenoid valve is arranged on the second branch pipe.

7. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 6 is characterized in that: The wastewater treatment device comprises a conical treatment tank, an upper opening opened at the top of the treatment tank, a plurality of ultrasonic devices arranged on the inner wall of the treatment tank, an aeration device arranged in the middle of the treatment tank, a gas treatment device arranged at the upper opening, a water outlet pipe arranged above the side of the treatment tank, a water inlet pipe arranged below the side of the treatment tank, and a mud discharge pipe arranged at the bottom of the treatment tank; The mud discharge pipe is provided with a mud discharge valve; The aeration device includes an air intake main pipe inserted into the treatment tank through an upper opening and a plurality of air intake branch pipe units connected to the air intake main pipe at uniform intervals in a vertical direction. The air intake branch pipe units include a plurality of air intake branch pipes annularly connected to the air intake main pipe, and a plurality of air intake holes are opened on the air intake branch pipes.

8. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 7 is characterized in that: The water outlet pipe is provided with a filter membrane assembly, the filter membrane assembly is connected to a clean water drainage pipe and a concentrated water return pipe, and the end of the concentrated water return pipe is connected to the water inlet pipe; The ultrasonic device comprises an ultrasonic generator and an ultrasonic transducer connected to the ultrasonic generator, and the ultrasonic transducer is located between the water inlet pipe and the water outlet pipe in the vertical direction.

9. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 1 is characterized in that: The micro-nano water supply pipeline is provided with a dosing device and a water diversion pump.

10. The wastewater intelligent treatment system combining ozone and micro-nano bubbles according to claim 1 is characterized in that: The system also includes a monitoring device, which is arranged on the wastewater treatment device and is used at least to monitor the conductivity and COD concentration of the wastewater.

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