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CN-122010231-A - Catalytic-ultrasonic cooperative treatment process and system for targeted degradation of formaldehyde in wastewater

CN122010231ACN 122010231 ACN122010231 ACN 122010231ACN-122010231-A

Abstract

The application relates to the technical field of industrial wastewater treatment, in particular to a catalytic-ultrasonic cooperative treatment process and system for degrading formaldehyde in wastewater in a targeted manner, which are used for solving the problems of no selectivity, high energy consumption, weak impact resistance and poor long-period stability in the treatment of high-concentration formaldehyde wastewater in the related technology. The system comprises a reactor main body, a catalyst unit, an array type ultrasonic unit, an intelligent regulation and control unit and an auxiliary unit, wherein the units are coordinated through structure assembly linkage and signal transmission to form a full-closed-loop integrated processing system of data acquisition, prediction calculation, instruction execution and feedback correction. The application can solve the technical problems of unstable formaldehyde degradation efficiency, high energy consumption, weak impact resistance and poor extreme working condition adaptation in the prior art in a mode of two-dimensional partition adaptation, double-drive cavitation coordination, intelligent closed-loop regulation and control and unit integration coordination.

Inventors

  • ZHANG GUANGYUAN
  • LI YUANYUAN

Assignees

  • 北京中科国益环保工程有限公司

Dates

Publication Date
20260512
Application Date
20260314

Claims (10)

  1. 1. The catalytic-ultrasonic cooperative treatment system for the targeted degradation of formaldehyde in wastewater is characterized by comprising a reactor main body, a catalyst unit, an array ultrasonic unit, an intelligent regulation and control unit and an auxiliary unit, wherein the units cooperate through structure assembly linkage and signal transmission to form a full-closed-loop integrated treatment system of data acquisition, prediction calculation, instruction execution and feedback correction; The catalyst unit comprises a 3X 2 double-dimensional partition catalyst tube and a 3X 2 double-dimensional partition acoustic focusing catalyst module which are coaxially assembled and integrated, wherein the 3X 2 double-dimensional partition acoustic focusing catalyst module is nested inside the 3X 2 double-dimensional partition catalyst tube, the 3X 2 double-dimensional partition is divided into a lower high concentration area, a middle transition area and an upper low concentration area according to the ratio of 1:1:1 in the axial direction according to the 3 partition and the radial direction, the lower high concentration area, the middle transition area and the upper low concentration area are divided into a central area and an edge area according to the radius of 3:2 in the radial direction, six independent catalyst units are formed, and each partition is isolated by adopting a fluororubber miniature sealing ring with the thickness of less than 0.5 mm; Each partition of the 3X 2 two-dimensional partition acoustic focusing catalyst module is provided with an independent micro piezoelectric driving mechanism and a catalytic coating, wherein the catalytic coating is sequentially provided with an active catalytic sub-coating, an acoustic metamaterial nested layer and a salt-resistant sound transmission coating from inside to outside, the active catalytic sub-coating comprises a multi-level aperture cavitation nest, pt active sites and a microcapsule type self-repairing agent, the multi-level aperture cavitation nest is a PMMA-PNIPAM-PZT composite system, and the aperture distribution is 1-2 mu m, 2-4 mu m, 4-5 mu m=1:2:1; The array type ultrasonic unit consists of an ultrasonic generator and an array type transducer, the array type transducer adopts a lower coupling installation mode and corresponds to the 3X 2 double-dimensional partition catalyst tubes one by one, the partition independent frequency modulation and power modulation can be realized, the frequency modulation range is 20-1000kHz, and the power modulation range is 0.2-1W/mL; The intelligent regulation and control unit takes a PLC controller as a core, is provided with at least 16 paths of multi-channel interfaces and is respectively connected with 6 two-dimensional partition spectrum sensors, a micro electric field control module, an LSTM prediction algorithm module and an energy optimization algorithm module; The auxiliary unit comprises a circulating cooling water temperature control module, an enhanced backwashing module and a fault diagnosis module, wherein the temperature control range of the circulating cooling water temperature control module is 40-70 ℃, the temperature control precision is +/-0.5 ℃, the backwashing pressure of the enhanced backwashing module is 0.5-0.7MPa, and the backwashing duration is 4-6min.
  2. 2. The system of claim 1, wherein the 3 x 2 double-dimensional partition catalyst tube is wound with spiral microelectrodes with a pitch of 4-6mm and a wire diameter of 0.08-0.12mm, the voltage adjustment range of the microelectrodes is 5-10V, the power is less than 1W, the microelectrodes and the micro piezoelectric driving mechanism share a 12V power supply loop, the microelectrodes and the active catalytic sub-coating on the inner wall of the catalyst tube are controlled by a PLC shunt, a closed electric field loop is formed between the microelectrodes and the active catalytic sub-coating on the inner wall of the catalyst tube, PZT nanocrystals in the coating are used as an electric field response medium, and the telescopic adjustment and control of the PZT nanocrystals are realized by the voltage change of the electrode.
  3. 3. The system of claim 1, wherein the 3 x 2 two-dimensional partition acoustic focusing catalyst module has a micro piezoelectric driving mechanism with a power of less than 3W, a telescopic stroke of 0-4mm, and is capable of driving a transition structural surface to elastically deform to realize continuous adjustment within a focal length of 6-10mm, the transition structural surface is made of a flexible metal film or a composite material, an acoustic metamaterial nested layer is fixed on the transition structural surface, and a titanium alloy micro-column array structure with a column diameter of 5-20 μm and a height of less than 40 μm is adopted, so that the focal alignment precision with a cavitation nest is less than or equal to +/-0.2 mm.
  4. 4. The system of claim 1, wherein the microcapsule type self-repairing agent of the active catalytic sub-coating has a particle size of 0.8-1.2 μm, the wall material is polyurea formaldehyde, the core material is a mixed solution of tetrabutyl titanate and tetraethoxysilane=1:2, the Pt active site is loaded by an isovolumetric impregnation method, the Pt loading amount of the inner wall of the cavitation nest is 1.2-1.6wt%, the Pt loading amount of the edge area is 0.7-1.1wt%, and the average value of the Pt loading amount of the whole coating is 0.8-1.2wt%; optionally, the carrier of the active catalytic subcoating is parabolic, with a polishing accuracy ra=0.15-0.20 μm, and a focal length reference value of 7-9mm.
  5. 5. The system of claim 1, wherein the salt-resistant sound-transmitting coating is prepared by mixing fluorine modified silicone rubber and nano zirconia in a weight ratio of 6:4-8:2, adding 0.4-0.6% PVP dispersant, curing at 115-125 ℃ for 25-35min to form, wherein the thickness is less than 20 μm, and the salt adhesion amount is <3mg/cm2.
  6. 6. The system according to claim 1, wherein the response time of the two-dimensional partition spectrum sensor is less than 3s, the sampling frequency is not more than 1s, the LSTM prediction algorithm module is trained based on historical data of not less than 1000 hours, the concentration change trend can be predicted 20s in advance, the prediction error is not more than +/-8%, the micro electric field control module comprises 6 independent branch control units, and the response time is not more than 3s.
  7. 7. A catalytic-ultrasonic co-treatment process for targeted degradation of formaldehyde in wastewater, characterized by adopting the system of any one of claims 1-6, comprising the following four-stage core flow: S1, targeted adsorption and activation, namely, after diversion pretreatment, formaldehyde-containing wastewater flows into a 3X 2 two-dimensional partition acoustic focusing catalyst module from bottom to top, targeted adsorption and activation of formaldehyde is realized through Pt active sites of an active catalyst coating, the adsorption rate is more than or equal to 90%, and the retention rate of other biochemical COD components is more than or equal to 99.3%; S2, cavitation degradation, namely starting an array type ultrasonic unit, and realizing resonance matching of the aperture of the cavitation nest and ultrasonic frequency by means of a sound-heat passive response and an electric field active correction dual-drive mechanism of a cavitation nest of a PMMA-PNIPAM-PZT composite system, so as to cooperatively trigger cavitation effect to generate OH free radicals, and degrading formaldehyde activation intermediates into CO 2 and H 2 O; S3, intelligent collaborative optimization, wherein the intelligent regulation and control unit realizes four-dimensional linkage collaborative optimization of focal length, ultrasonic parameters and energy distribution through an LSTM prediction algorithm module and an energy optimization algorithm module based on real-time concentration data of the two-dimensional partition spectrum sensor; S4, temperature control and self-cleaning, wherein the temperature of the reaction is maintained stable through a circulating cooling water temperature control module, and the on-line self-cleaning is realized by combining the reinforced backwashing module and the catalyst self-repairing function, so that the wastewater reaches the discharge standard; The process adopts a double-dimensional partition active gradient adaptation design, a cavitation nest acoustic-electric double-drive cooperative mechanism, ultrasonic-catalytic-electric field multi-field coupling and energy redundancy dynamic distribution, and has the core process parameter range of 6-10mm of focal length, 20-1000kHz of ultrasonic frequency, 0.2-1W/mL of power density, 40-70 ℃ of reaction temperature, 60-120min of residence time and 3-12m/h of empty tower flow rate.
  8. 8. The process according to claim 7, wherein the 3X 2 two-dimensional partition water flow parameters are that the air tower flow rate is 3-12m/h and the residence time is 60-120min, and different concentration formaldehyde wastewater adopts differential parameter combination: (1) The formaldehyde with high concentration is 5000-12000mg/L, and the formaldehyde concentration range is 5000mg/L, and the adopted parameter combination strategy is 6-7mm of focal length, 20-40kHz of ultrasonic frequency and 0.35-0.45W/mL of power density; (2) Formaldehyde with medium concentration is 500-5000mg/L, the formaldehyde concentration range is 500mg/L, the formaldehyde does not contain 500mg/L, and the adopted parameter combination strategy is that the focal length is 7-8mm, the ultrasonic frequency is 40-100kHz, and the power density is 0.4-0.5W/mL; (3) Formaldehyde with low concentration is 30-500mg/L, and the adopted parameter combination strategy is that the focal length is 9-10mm, the ultrasonic frequency is 100-500kHz, and the power density is 0.55-0.6W/mL; Optionally, under the high-salt working condition and TDS 3-50000mg/L, the anti-salt sound transmission coating is used for protection, and meanwhile, the focusing parameter compensation of the acoustic metamaterial is linked, so that the focusing efficiency is ensured to be not lower than 95% under the condition that the TDS is less than or equal to 50000 mg/L.
  9. 9. The process according to claim 7, wherein the double driving mechanism of the cavitation nest is characterized in that under the working condition that the frequency is 20-40kHz, PNIPAM swells to increase the aperture by 10%, under the working condition that the frequency is 40-100kHz, PNIPAM is in a stable swelling state, under the working condition that the frequency is 100-400kHz, PNIPAM is in a stable transition state, under the working condition that the frequency is 400-500kHz, PNIPAM phase transition shrinkage reduces the aperture by 8%, and PZT nanocrystalline expansion and contraction are driven by a 5-10V micro-electric field to conduct active fine adjustment, the aperture adjustment precision is +/-0.01 mu m, and the matching error is <1%.
  10. 10. The process according to claim 7, characterized in that the four-dimensional linkage co-optimization is specifically: (1) Triggering focal length adjustment to +/-0.25-0.3 mm and power adjustment to +/-0.04-0.05W/mL when the partition concentration fluctuates by +/-10%; (2) The concentration trend is predicted 20s in advance, and parameter presetting is realized, feedback fine adjustment is carried out by taking 3s as a period, and the response time is less than or equal to 3s; (3) When the water inflow concentration is suddenly changed by +/-50%, a quick response program is started, and the whole system parameter adaptation is completed within 8-10 seconds; (4) When the energy efficiency ratio deviation of adjacent subareas is less than 5%, an energy linkage mode is started, 10-12% redundant energy of an upper part area is transferred to a lower part high concentration area, and when the concentration of formaldehyde in effluent is less than 8mg/L and the formaldehyde is stable for 25-30s, an energy saving mode is triggered, so that the overall energy consumption is reduced by 8-12%; (5) Automatically executing the self calibration of the zone focal length every 280-320 hours of operation, and controlling the reference value to be 8mm and the calibration deviation to be less than or equal to +/-0.1 mm; Optionally, the self-cleaning triggering condition is that the pressure drop of each 180-220h or the catalyst tube array is suddenly changed to be more than 0.2kPa, the reverse flushing and the ultrasonic low-power collaborative cleaning are adopted, the backwashing pressure is 0.5-0.7MPa, the backwashing time is 4-6min, and when the active catalytic sub-coating generates microcracks, the microcapsule cracks to release the core material to crosslink and solidify so as to realize self-repairing, and the repairing efficiency is more than 90%.

Description

Catalytic-ultrasonic cooperative treatment process and system for targeted degradation of formaldehyde in wastewater Technical Field The application relates to the technical field of industrial wastewater treatment, in particular to a catalytic-ultrasonic cooperative treatment process and system for targeted degradation of formaldehyde in wastewater. Background In the industrial production process, a large amount of wastewater containing formaldehyde is generated, the formaldehyde has strong toxicity and carcinogenicity, and if the formaldehyde is directly discharged, serious harm is caused to the ecological environment and human health, so the efficient degradation treatment of the formaldehyde in the wastewater is an important research direction in the field of industrial wastewater treatment. At present, the catalytic-ultrasonic cooperative technology has the advantages of high degradation efficiency, no secondary pollution and the like, becomes one of the main flow technologies for wastewater formaldehyde treatment, and is widely applied to various industrial wastewater treatment scenes. In the prior art, the scheme of catalytic-ultrasonic cooperative treatment of formaldehyde wastewater mostly adopts a single-dimensional partition design, cavitation nest mostly adopts a passive acoustic response mode, a regulation and control system mainly adopts simple feedback control, and all units of the treatment system are mostly in distributed combination. In the practical application process, the scheme generally carries out degradation reaction by fixing ultrasonic parameters and focal length, and the energy distribution adopts an integral regulation mode and does not dynamically adapt to different concentration partitions. However, the prior art has the defects that firstly, the concentration gradient distribution of formaldehyde in wastewater cannot be accurately adapted by a single-dimensional partition design, so that partial degradation is insufficient or energy redundancy is wasted, secondly, the adaptive frequency range of a passive cavitation response mode is narrow, the cavitation efficiency is low, the targeted degradation of formaldehyde is difficult to realize, thirdly, the response of a regulating system is delayed, the shock resistance is weak, the working condition of abrupt change of the concentration of industrial wastewater cannot be met, fourthly, effective adaptation measures aiming at extreme working conditions such as high salt, long-period running and the like are lacking, the treatment stability is poor, thirdly, the system unit has poor cooperativity, the process cannot be guaranteed to fall to the ground, the complex industrial wastewater with the formaldehyde concentration and the salinity which are greatly fluctuated is difficult to adapt, and finally, the formaldehyde degradation efficiency is unstable, the energy consumption is high, and the application range is limited. Disclosure of Invention The application provides a catalytic-ultrasonic cooperative treatment process and system for targeted degradation of formaldehyde in wastewater, which can solve the technical problems of unstable formaldehyde degradation efficiency, high energy consumption, weak impact resistance and poor extreme working condition adaptation in the prior art in a mode of two-dimensional partition adaptation, double-drive cavitation cooperation, intelligent closed-loop regulation and control and unit integration cooperation. In a first aspect, the application provides a catalytic-ultrasonic co-treatment system for targeted degradation of formaldehyde in wastewater, which adopts the following technical scheme: A catalytic-ultrasonic cooperative treatment system for targeted degradation of formaldehyde in wastewater comprises a reactor main body, a catalyst unit, an array ultrasonic unit, an intelligent regulation and control unit and an auxiliary unit, wherein the units cooperate through structure assembly linkage and signal transmission to form a full-closed-loop integrated treatment system of data acquisition, prediction calculation, instruction execution and feedback correction; The catalyst unit comprises a 3X 2 double-dimensional partition catalyst tube and a 3X 2 double-dimensional partition acoustic focusing catalyst module which are coaxially assembled and integrated, wherein the 3X 2 double-dimensional partition acoustic focusing catalyst module is nested inside the 3X 2 double-dimensional partition catalyst tube, the 3X 2 double-dimensional partition is divided into a lower high concentration area, a middle transition area and an upper low concentration area according to the ratio of 1:1:1 in the axial direction according to the 3 partition and the radial direction, the lower high concentration area, the middle transition area and the upper low concentration area are divided into a central area and an edge area according to the radius of 3:2 in the radial direction, six independent catalyst units ar