CN114984746A - System method and device for treating VOCs waste gas in disinfectant and aquaculture wastewater pool - Google Patents

System method and device for treating VOCs waste gas in disinfectant and aquaculture wastewater pool Download PDF

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CN114984746A
CN114984746A CN202210939431.9A CN202210939431A CN114984746A CN 114984746 A CN114984746 A CN 114984746A CN 202210939431 A CN202210939431 A CN 202210939431A CN 114984746 A CN114984746 A CN 114984746A
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gas
lysozyme
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wastewater
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CN114984746B (en
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王金鹤
牛文雅
李鸥阳
张双
王琳
陈飞勇
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Shandong Jianzhu University
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Abstract

The invention provides a sterilizing agent and a method and a device for treating VOCs waste gas in a culture wastewater pool, belongs to the technical field of biology, and particularly relates to sterilization of resistant microorganisms in a treatment system for VOCs waste gas generated in the purification process of culture wastewater. The method mainly solves the problems of ecological risks and public health safety caused by the fact that a treatment system contains a large number of resistant microorganisms due to antibiotics contained in VOCs aerosol of the existing aquaculture wastewater tank, utilizes the efficient killing effect of surfactant modified bacteriolytic peptide on the resistant microorganisms and the advantage that the surfactant modified bacteriolytic peptide cannot induce resistance, integrates the triple advantages of modified bacteriolytic peptide, modified kaolin gel and a catalytic ozone oxidation process, and improves the quality of gas emission. Meanwhile, the micron-sized modified bacteriolytic peptide spray generated under ultrasonic vibration is utilized, the killing extent and the killing efficiency of resistant microorganisms in the system are improved, and the content of the resistant microorganisms contained in the aerosol is obviously reduced. The invention can be used for treating VOCs, odor and aerosol wrapped with antibiotics and resistant microorganisms.

Description

System method and device for treating VOCs waste gas in disinfectant and aquaculture wastewater pool
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a method and a device for a system for treating VOCs waste gas in a disinfectant and culture wastewater pond.
Background
With the rapid development of large-scale livestock and poultry breeding industry, a large amount of livestock and poultry manure polluted by feed additives and veterinary drug residues is generated, so that malodorous gas is dissipated from water due to the violent turbulent motion of water flow in the treatment process of breeding wastewater, and a part of antibiotics is discharged along with aerosol. The part of gas causes high accumulated concentration of antibiotics, resistant microorganisms, resistant genes and other micro pollutants in the cultivation wastewater treatment structure, and the risk of spreading the resistant genes of the resistant microorganisms from the livestock and poultry farm to the surrounding environment exists.
At present, the treatment technology aiming at VOCs waste gas generated by aquaculture waste water is more, and the treatment technology mainly adopts single or combined process with alkali liquor absorption, catalytic oxidation and biological deodorization as main bodies. However, these types of processes are directed to the air or exhaust gas to be disinfected and have little effect on the treatment of the high concentrations of resistant microorganisms that accumulate within the structure itself. In the prior art, such as spraying disinfection of the disinfectant, the particle size of liquid drops is large (0.5-4 mm), and the disinfectant is low in distribution efficiency under the condition of limited using amount of the medicament and cannot be fully contacted with air and resistant microorganisms in the device. When the copy number of resistant microorganisms and resistant genes in the culture wastewater pool is higher, a more convenient and effective method for thoroughly killing the resistant microorganisms in the waste gas and waste gas treatment device is urgently needed.
Lysozyme is a biological agent, and can destroy resistant microbial cells through hydrolysis, so that the cell walls of thalli are dissolved to kill bacteria. The lysozyme can be directly combined with virus protein with negative charge to form a complex with DNA, RNA and apoprotein, so that the virus carrying the resistance gene is inactivated. Most importantly, lysozyme sterilizes by breaking cell walls, in contrast to the sterilization mechanism of antibiotics, without conferring resistance to other microorganisms. Therefore, the lysozyme is used for killing resistant microorganisms in the VOCs waste gas treatment system of the culture wastewater tank, and is a green, environment-friendly and safe bactericide. However, the water solubility and fat solubility of the common lysozyme are limited, and when the common lysozyme is used for treating the atmospheric VOC in the environmental field, the common lysozyme is difficult to permeate into aerosol to directly react with resistant microorganisms, so that the killing efficiency is not ideal.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a sterilizing agent and a system and a device for treating VOCs waste gas in a culture wastewater pond.
The technical scheme of the invention is realized by the following modes:
the culture wastewater is analyzed based on the large-scale culture industry, the flora structure in the culture wastewater treatment process is related to the treatment process, for example, the dominant phyla of the bacterial flora of the sewage collecting tank and the anaerobic reactor are bacteroidetes, firmicutes, proteobacteria and the aeration tank, and the dominant phyla of the bacterial flora also comprises microbacteria, candida and the like. The key point is that the breeding wastewater contains sulfamethoxazole, sulfamonomethoxine, doxycycline, oxytetracycline and other antibiotic substances, and the sewage contains species such as sulfamethoxazole, sulfamonomethoxine, doxycycline and oxytetracyclinePetrimonas、Lachnospiracea_incertae_sedis、Clostridium XlVa、TissierellaThe like are extremely susceptible to resistance, and some can produce plasmids containing resistance genes. Therefore, the invention aims to treat VOCs waste gas generated in the culture wastewater purification process and kill resistant microorganisms.
The invention relates to a killing agent, which is formed by modifying and synthesizing lysozyme, and adopts the coupling of far infrared radiation and a surfactant to ensure that the lysozyme generates resonance under the condition of far infrared radiation and promote the combination of the surfactant and the lysozyme, wherein the combination state of the lysozyme and the surfactant can improve the diffusion efficiency of the lysozyme in gas molecules and aerosol and the combination efficiency of the lysozyme and resistant microorganisms to be killed; the modified lysozyme is modified and synthesized to obtain the modified lysozyme reinforced disinfectant.
The surfactant is alkyl glycoside surfactant.
The preparation method of the sterilizing agent comprises the following steps: preparing 0.01mmol/mL alkyl glycoside aqueous solution, slowly dripping 0.1mmol/mL alkyl glycoside aqueous solution into lysozyme solution with the mass concentration of about 50mg/mL under the condition of far infrared radiation with the wavelength of 4-14 microns, and continuously stirring for 20-40 min in the whole process; in the process, far infrared radiation is carried out intermittently, namely the radiation time per minute is 5 s; finally obtaining a clear mixed solution of alkyl glycoside and lysozyme with the molar ratio of about 1: 8-1: 10; centrifuging the mixed solution, washing off floating foam, and freeze-drying in vacuum to constant weight to obtain the modified lysozyme reinforced disinfectant.
The invention discloses a VOCs waste gas treatment system method of a culture wastewater pond, which comprises the following steps: aiming at VOCs waste gas in a culture wastewater pool, particularly aiming at resistant microorganisms in the waste gas, the sterilizing agent is utilized to generate micron-sized modified lysozyme spray under ultrasonic vibration to sterilize the waste gas, particularly to efficiently sterilize the resistant microorganisms in the waste gas, so that the sterilizing breadth and the sterilizing efficiency of the resistant microorganisms in a waste gas system can be improved, the content of the resistant microorganisms contained in waste gas aerosol is reduced, and the resistance cannot be induced in the waste gas; and the exhaust gas is treated by combining the triple processes of modified lysozyme, modified kaolin gel and catalytic ozonation, so that the exhaust emission quality is improved.
A wastewater pool gas-collecting hood is additionally arranged above the breeding wastewater pool, a modified lysozyme ultrasonic spraying device is arranged in the hood, waste gas generated by wastewater is sterilized, the sterilized waste gas is collected above the wastewater pool gas-collecting hood, and the sterilized waste gas is dredgedAlkaline absorption is carried out on the waste gas in the modified kaolin gel alkaline absorption unit, and the waste gas in the unit is subjected to sterilization treatment by ultrasonic spraying of modified lysozyme in the absorption process; the unit waste gas is dredged to HfOx/SiO 2 The catalytic ozone oxidation unit is used for carrying out catalytic ozone oxidation treatment on the waste gas in the unit, and the waste gas in the unit is subjected to sterilization treatment by ultrasonic spraying of modified lysozyme in the oxidation process; and finally, discharging the waste water out of the environment.
A gas-collecting hood (1) of the wastewater pool, a modified lysozyme spray generator (2), a modified kaolin gel alkaline absorption unit (3), HfOx/SiO 2 A catalytic ozonation unit (4);
an aeration pipeline (6) is arranged at the bottom of the culture wastewater tank (5), aeration heads (7) are distributed on the pipe body of the aeration pipeline (6), and an air blower (8) outside the tank is connected to the upstream of the aeration pipeline (6);
an aeration system in the culture wastewater tank (5) is formed by the blower (8), the aeration pipeline (6) and the aeration head (7);
a waste water pool gas-collecting hood (1) is buckled above the mouth of the culture waste water pool (5) by a sealing hood; the waste water pool gas-collecting hood (1) is provided with a bulge which is arched upwards, and the space in the hood of the waste water pool gas-collecting hood (1) and the space above the waste water liquid level of the breeding waste water pool (5) form a waste gas treatment space;
modified lysozyme spray generators (2) are arranged between the peripheries of the openings of the culture wastewater ponds (5) of the wastewater pond gas-collecting hood (1), and the modified lysozyme spray generators (2) are distributed in pairs in opposite directions; an ultrasonic system (14) and a modified lysozyme turbid liquid storage cavity (15) are arranged in the modified lysozyme spray generator (2); the modified lysozyme suspension storage cavity (15) is filled with the disinfectant, and an ultrasonic system (14) of the modified lysozyme spray generator (2) covers the waste gas treatment space;
a plurality of gas collection bellmouths (9) are arranged in a dome of a gas collection hood (1) of the wastewater pool, the gas collection bellmouths (9) are converged and communicated to a gas collection main pipe (12) through gas collection branch pipes (10), and the gas collection main pipe (12) extends and is communicated to the bottom space of the inner cavity of a modified kaolin gel alkaline absorption unit (3) outside the gas collection hood (1) of the wastewater pool;
the middle layer of the inner cavity of the modified kaolin gel alkaline absorption unit (3) is filled with organic phosphonic acid modified kaolin gel (20) soaked by KOH solution;
the first modified lysozyme spray header (21) is arranged at the top of the inner cavity of the modified kaolin gel alkaline absorption unit (3);
the filler space of the organic phosphonic acid modified kaolin gel (20) soaked by the KOH solution forms a filler mass transfer and sterilization channel of cross flow spraying of the alkaline absorption unit;
the top layer of the inner cavity of the modified kaolin gel alkaline absorption unit (3) is provided with an alkaline absorption unit gas collection bell mouth (22), and the alkaline absorption unit gas collection bell mouth (22) is communicated to HfOx/SiO through an alkaline absorption unit exhaust pipe (23) 2 A bottom cavity of the catalytic ozone oxidation unit (4);
HfOx/SiO 2 a plurality of groups of HfOx/SiO are uniformly and fixedly distributed in the inner cavity of the catalytic ozonation unit (4) 2 A catalyst (25) suspension;
an ozone supply pipe (26) of the ozone generator (27) is communicated with HfOx/SiO 2 A bottom cavity of the catalytic ozone oxidation unit (4);
HfOx/SiO 2 the top of the inner cavity of the catalytic ozone oxidation unit (4) is provided with a second modified lysozyme spray header (28);
multiple sets of HfOx/SiO 2 The catalyst (25) suspension space forms a mass transfer oxidation killing channel of cross-flow spraying of the ozone oxidation unit;
HfOx/SiO 2 an ozone oxidation gas-collection bell mouth (29) is arranged in the top space of the inner cavity of the catalytic ozone oxidation unit (4), the ozone oxidation gas-collection bell mouth (29) is connected with an external air pump (31) through an oxidation unit exhaust pipe (30), and the air pump (31) exhausts air to the outside.
The waste gas treatment process of the system device comprises the following steps:
under the condition that an aeration head (7) at the bottom of a culture wastewater pool (5) provides oxygen, organic pollutants in wastewater are degraded and metabolized, the water quality of the wastewater is purified, and a part of waste gas is generated; meanwhile, under the blowing-off action of the aeration head (7), VOCs waste gas containing antibiotics is dissipated to the upper part of the wastewater treatment tank (5) and the inside of the gas-collecting hood (1) of the wastewater treatment tank;
waste gas is collected through a plurality of gas-collecting bell mouths (9), and then passes through a gas-collecting branch pipe (10) and a gas-collecting main pipe (12) to penetrate out of a waste water tank gas-collecting hood (1) and enter a modified kaolin gel alkaline absorption unit (3);
carbon dioxide and most organic matters in the waste gas are absorbed by organic phosphonic acid modified kaolin gel KOH absorption liquid, and residual waste gas enters HfOx/SiO through an alkaline absorption unit exhaust pipe (23) after being collected through a gas collection bell mouth (22) of the alkaline absorption unit at the top 2 A catalytic ozonation unit (4);
HfOx/SiO 2 residual VOCs and a small amount of antibiotics in the waste gas in the catalytic ozone oxidation unit (4) are quickly degraded and converted under the oxidation action of ozone provided by an ozone generator (27) and an ozone supply pipe (26); the purified air is pumped away by an external air pump (31);
the killing process of the system device parallel to the waste gas treatment process is as follows:
the modified lysozyme turbid liquid storage cavity (15) in the modified lysozyme spray generator (2) generates water atomized liquid drops of 0.5-10 micrometers under the high-frequency vibration of the ultrasonic system (14); the modified lysozyme component is dispersed in the waste water pool gas-collecting hood (1), the modified kaolin gel alkaline absorption unit (3) and HfOx/SiO 2 The corners of the space and the inner surface in the catalytic ozone oxidation unit (4) achieve the aim of killing resistant microorganisms;
and the ultrasonically atomized water atomized modified lysozyme drops in the space in the gas collecting hood (1) of the wastewater pool, the space in the modified kaolin gel alkaline absorption unit (3), HfOx/SiO 2 The space in the catalytic ozone oxidation unit (4) forms stepwise killing of the waste gas treatment process.
The vibration band frequency of an ultrasonic system (14) in the modified lysozyme spray generator (2) is 1.6-2.0 MHz, the concentration of modified lysozyme in the modified lysozyme suspension storage cavity (15) is 5wt%, and the working temperature is 5-40 ℃;
modified lysozyme spray generator (2) is discontinuous operation, and its operational mode is set for according to breeding the waste water treatment capacity by operating technical personnel, and under the general condition, the operating time ratio of waste water treatment pond (5) and modified lysozyme spray generator (2) is 24 h: 0.5 h;
the modified kaolin gel alkaline absorption unit (3) contains 1wt% of KOH and 10wt% of organic phosphonic acid modified kaolin gel; the kaolin gel modified by organic phosphonic acid needs to be prepared in advance, the organic phosphonic acid is diethylenetriamine pentamethylene phosphonic acid, and the kaolin is modified in an NaOH alkaline environment;
HfOx/SiO 2 the catalyst in the catalytic ozone oxidation unit (4) is HfOx/SiO 2 Is prepared by self-assembling SiO 2 Growing HfOx catalyst on the surface in situ; the catalyst packing was about 10%.
The application of the disinfectant in the waste gas disinfecting treatment process is disclosed.
The invention discloses an application of a VOCs waste gas treatment system method of a culture wastewater pond in a waste gas disinfection treatment process.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a sterilizing agent and a method and a device for treating VOCs waste gas in a culture wastewater pond, aiming at solving the problems of ecological risk and public health safety caused by the fact that a treatment system contains a large number of resistant microorganisms due to antibiotics contained in VOCs aerosol of the existing culture wastewater pond. Meanwhile, the micron-sized modified lysozyme spray generated under ultrasonic vibration is utilized, so that the killing extent and the killing efficiency of resistant microorganisms in the system are improved, and the content of the resistant microorganisms contained in the aerosol is obviously reduced. The device for killing resistant microorganisms in the VOCs waste gas treatment system of the culture wastewater tank comprises a wastewater tank gas-collecting hood and modified bacteria dissolvingEnzyme spray generator, modified kaolin gel alkaline absorption unit and HfOx/SiO 2 Catalytic ozonation unit, gas conveying device and fan. The invention can be used for treating VOCs, odor and aerosol wrapped with antibiotics and resistant microorganisms generated in the process of treating the general aquaculture wastewater.
The invention adopts the surfactant to carry out chemical modification on the common lysozyme under the condition of far infrared radiation vibration, and compared with the common lysozyme and the lysozyme modified by the surfactant, the mass transfer efficiency of the obtained modified lysozyme in an organic phase and a water phase is obviously improved, thereby improving the contact and killing efficiency of antagonistic microorganisms. In addition, the method adopts an ultrasonic method to carry out water atomization treatment on the modified lysozyme bactericide to form liquid drops with micron or even nanometer particle size, thereby greatly improving the application efficiency of the bactericide and carrying out omnibearing sterilization and killing of resistant microorganisms from each unit generated and treated by VOCs waste gas; waste gas treatment equipment is optimized in a targeted mode, the degradation efficiency of organic matters and the killing efficiency of resistant microorganisms are improved, the waste gas treatment process is simplified, labor operation is reduced, and VOCs waste gas in the culture waste water tank can be discharged into the atmosphere after being treated.
The invention has the advantages that:
firstly, the invention modifies kaolin with organic phosphonic acid to prepare gel, which improves the adsorption capacity of kaolin to VOCs.
Secondly, the ozone oxidation unit adopts HfOx/SiO 2 The catalyst has high catalytic efficiency and can realize the high-efficiency oxidation of VOCs.
Introducing modified lysozyme atomizing device in breeding wastewater disposal basin VOCs exhaust-gas treatment system, through the modified lysozyme solution atomizing particle of micron order that produces under the supersound high frequency vibration, the resistance microorganism to each unit inside of exhaust-gas treatment system disappears and kills, all is effective to bacterium and virus, high-efficient, green, with low costs, and most importantly, can not make the microorganism further produce the resistance.
And fourthly, chemically modifying the lysozyme by adopting a new modification method, namely a novel nonionic surfactant alkyl glycoside coupled far infrared radiation vibration condition, so that the obtained modified lysozyme has better water solubility and fat solubility. Improves the mass transfer efficiency of the lysozyme in an organic phase and a water phase, and obviously strengthens the killing effect. The invention has the advantages that the structure of the plurality of components is simple, the components supplement each other and complement each other in advantages, the high-efficiency treatment of the VOCs waste gas in the cultivation waste water can be realized, particularly, the content of resistant microorganisms and the copy number of resistant genes can be effectively reduced, and the possibility that a cultivation farm becomes an ecological risk and an infectious disease source is reduced.
The device for killing resistant microorganisms in the VOCs waste gas treatment system of the aquaculture wastewater pond realizes the adsorption of VOCs, the removal of VOCs and the killing of the resistant microorganisms in the treatment system, and is respectively composed of a modified kaolin gel alkaline absorption unit and HfOx/SiO 2 A catalytic ozone oxidation unit and a modified lysozyme spray generator. Firstly, VOCs gas containing antibiotics is generated in a culture wastewater (aerobic) pool, the VOCs gas is collected through a gas-collecting bell mouth at the top of a gas-collecting hood of the wastewater pool, after the VOCs gas enters a modified kaolin gel alkaline absorption unit, a part of VOCs is absorbed by organic phosphonic acid modified kaolin gel soaked by KOH solution, and residual VOCs enter HfOx/SiO along with the gas 2 A catalytic ozonation unit. HfOx/SiO 2 Adsorbing VOCs to the surface area of the catalyst to increase the contact probability of ozone and organic matters; at the same time, HfOx/SiO 2 Catalytically activate ozone molecules, improve ozone decomposition generation, improve O, oxidize VOCs and remove odor. The cultivation wastewater pool usually contains a part of antibiotic and veterinary drug residues, which are easy to generate resistant microorganisms and accumulate in a waste gas treatment system, so the invention is provided with the modified lysozyme spray generator, and the atomized modified lysozyme solution small particles are used for respectively killing the resistant microorganisms in the structures such as the interior of a wastewater pool gas collecting hood, the interior of a kaolin gel alkaline absorption unit, the interior of a catalytic ozone oxidation unit, an auxiliary pipeline and the like. In conclusion, by controlling specific operating conditions, such as kaolin gel concentration, ozone and catalyst content, particle size of modified lysozyme atomized particles and the like, removal of VOCs and killing of resistant microorganisms are realized, and treatment of VOCs waste gas of aquaculture wastewater is realized overall.
The method and the device for treating VOCs waste gas in the disinfectant and culture wastewater pond are reasonable in design, simple in structure, safe, reliable, convenient to use, easy to maintain and good in popularization and use value.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention.
The reference numerals in the drawings denote:
1. a gas collecting hood of the wastewater pool, 2, a modified lysozyme spray generator, 3, a modified kaolin gel alkaline absorption unit, 4, HfOx/SiO 2 A catalytic ozone oxidation unit,
5. a culture wastewater tank 6, an aeration pipeline 7, an aeration head 8 and a blower,
9. a gas collection bell mouth 10, a gas collection branch pipe 11, a tee joint 12, a gas collection main pipe 13 and sealing rubber,
14. an ultrasonic system 15, a modified lysozyme turbid liquid storage cavity,
16. an electric valve of the absorption unit 17, a gas collecting bypass pipe 18, an electric valve of a bypass 19, a vacuum pump,
20. an organophosphonic acid modified kaolin gel soaked with KOH solution,
21. a first modified lysozyme spray header 22, an alkaline absorption unit gas collection bell mouth 23, an alkaline absorption unit exhaust pipe 24, a first pressure stabilizing valve,
25. multi-group HfOx/SiO 2 The device comprises a catalyst, 26, an ozone supply pipe, 27, an ozone generator, 28, a second modified lysozyme spray head, 29, an ozone oxidation gas collection bell mouth, 30, an oxidation unit exhaust pipe, 31, an air pump, 32 and a second pressure stabilizing valve.
Detailed Description
The following detailed description of the method and the device for treating VOCs waste gas in a disinfectant and aquaculture wastewater tank according to the present invention will be made with reference to the accompanying drawings.
The first embodiment is as follows:
as shown in the attached drawings, the invention relates to a method and a device for treating VOCs waste gas in a disinfectant and aquaculture wastewater pond, wherein:
the disinfectant is the modification and synthesis of lysozyme, and adopts the coupling of far infrared radiation and a surfactant, so that the lysozyme generates resonance under the condition of the far infrared radiation, and the combination of the surfactant and the lysozyme is promoted, and the combination state of the surfactant and the lysozyme can improve the diffusion efficiency of the lysozyme in gas molecules and aerosol and the combination efficiency of the lysozyme and resistant microorganisms to be disinfected and killed; the modified lysozyme is modified and synthesized to obtain the modified lysozyme reinforced disinfectant;
the surfactant is alkyl glycoside surfactant;
the preparation method of the modified lysozyme reinforced disinfectant comprises the following steps: preparing 0.01mmol/mL alkyl glycoside aqueous solution, slowly dripping 0.1mmol/mL alkyl glycoside aqueous solution into 50mg/mL lysozyme solution under the condition of far infrared radiation with the wavelength of 4-14 microns, and continuously stirring for 20-40 min in the whole process; in the process, far infrared radiation is carried out intermittently, and the radiation time per minute is 5 s; finally obtaining a clear mixed solution with the molar ratio of the alkyl glycoside to the lysozyme being 1: 8-1: 10; centrifuging the mixed solution, washing off floating foam, and freeze-drying in vacuum to constant weight to obtain the modified lysozyme reinforced disinfectant.
The invention discloses a VOCs waste gas treatment system method of a culture wastewater pond, which comprises the following steps: aiming at VOCs waste gas in a culture wastewater pool, particularly aiming at resistant microorganisms in the waste gas, the sterilizing agent is utilized to generate micron-sized modified lysozyme spray under ultrasonic vibration to sterilize the waste gas, particularly to efficiently sterilize the resistant microorganisms in the waste gas, so that the sterilizing breadth and the sterilizing efficiency of the resistant microorganisms in a waste gas system can be improved, the content of the resistant microorganisms contained in waste gas aerosol is reduced, and the resistance cannot be induced in the waste gas; and the exhaust gas is treated by combining the triple processes of modified lysozyme, modified kaolin gel and catalytic ozonation, so that the exhaust emission quality is improved.
A wastewater pool gas-collecting hood is additionally arranged above the breeding wastewater pool, a modified lysozyme ultrasonic spraying device is arranged in the hood, waste gas generated by wastewater is subjected to sterilization treatment, the sterilized waste gas is collected above the wastewater pool gas-collecting hood and is dredged into a modified kaolin gel alkaline absorption unit to perform alkaline absorption on the waste gas, and a modified solvent is utilized in the absorption processCarrying out sterilization treatment on the waste gas in the unit by bacterial enzyme ultrasonic spraying; the unit waste gas is dredged to HfOx/SiO 2 The catalytic ozone oxidation unit is used for carrying out catalytic ozone oxidation treatment on the waste gas in the unit, and the waste gas in the unit is subjected to sterilization treatment by ultrasonic spraying of modified lysozyme in the oxidation process; and finally, discharging the waste water out of the environment.
The solubility of common lysozyme in water and the solubility of common lysozyme in fat are both limited, and the solubility of common lysozyme in water is respectively measured to be 9.98 g/L and 1.2g/100 g. In contrast, the solubility of the lysozyme modified by far infrared radiation in water is 20.17g/L, and the solubility in the rapeseed salad oil is 2.51g/100 g. Therefore, the lysozyme modified by the far infrared radiation has better water solubility and fat solubility, and is beneficial to mass transfer and diffusion in waste gas. The diffusion efficiency measured by the invention also proves that the diffusion rate of the common lysozyme is 2.6-3.1 mg/(min.m) within 1h of the operation of the lysozyme spray generator 3 ) The diffusion rate of the modified lysozyme is 4-6.5 mg/(min.m) 3 ). Therefore, the modified lysozyme has stronger killing efficiency on microorganisms (including pathogenic microorganisms). More importantly, the mass transfer to microorganisms in the aerosol cannot be realized due to the limited water solubility and fat solubility of the common lysozyme, and the killing efficiency cannot be improved by simply prolonging the reaction time of the common lysozyme.
TABLE 1 comparison of the Performance of ordinary lysozyme and IR-modified lysozyme
Figure DEST_PATH_IMAGE002
(in Table 1, the diffusion rate for the lysozyme spray generator was determined within 1 hour of the selection, because the results are more reasonable and effective within 1 hour. if it exceeds 1 hour, the diffusion rate after more than 1 hour is meaningless due to saturation of the diffusion profile, turbulence of the air flow, or even settling, and the influence of external conditions.)
In the process of generating waste gas in the waste water treatment pool, respectively before the operation of the modified lysozyme spray generator and after the operation is started, 0h. And at 1h, 5h, 12h and 24h, collecting waste gas samples in the gas collecting hood by means of 6 sampling points on the upper, lower and periphery in the gas collecting hood by means of the microbial aerosol collecting concentrator. Eluting a sample, and measuring the concentration of the bacteriolytic peptide by using a high performance liquid chromatograph; meanwhile, the other part is pretreated and then the shape of the microbial cells is observed by an electron microscope. The measurement result shows that the concentration of the bacteriolysin is 0 g/m in 0h, 1h, 5h, 12h and 24h 3 Exhaust gas, 0.18 to 0.21 g/m 3 Exhaust gas, 0.19 to 0.20 g/m 3 Exhaust gas, 0.18-0.20 g/m 3 Waste gas and 0.19-0.21 g/m 3 And (4) exhaust gas. Therefore, the bacteriolytic peptide can be diffused to all positions of the gas-collecting hood within 0.5h, the concentration difference of all positions is small, and the diffusion efficiency is high. After the lysozyme spray generator operates for 0 hour, 1 hour, 5 hours, 12 hours and 24 hours, the observed cell rupture ratios are respectively 0-1%, 47-51%, 80-82%, 91-92% and 95-97%. It can be seen that the efficiency of diffusion in the gas molecules, aerosol, and lysozyme binding to the resistant microorganisms to be killed is high.
The device comprises a waste water pool gas-collecting hood 1, a modified lysozyme spray generator 2, a modified kaolin gel alkaline absorption unit 3, HfOx/SiO 2 A catalytic ozonation unit 4.
The section of the waste water pool gas collecting hood 1 is arc-shaped and is covered on the surface of the square breeding waste water pool 5 by a cage around the edge of the waste water treatment pool 5. The culture wastewater 5 pond is generally provided with an aeration pipeline 6 and aeration heads 7, wherein one end of the aeration pipeline 6 is connected with a plurality of aeration heads 7, and the other end is connected with a blower 8. The top of the arc-shaped gas collecting hood of the wastewater pool 1 is provided with a plurality of gas collecting horn mouths 9, the gas collecting horn mouths are connected with gas collecting branch pipes 10, the two gas collecting branch pipes 10 are connected with a gas collecting main pipe 12 through a tee 11, and sealing rubber 13 is arranged at a hole of the gas collecting main pipe 12 penetrating out of the wastewater pool gas collecting hood 1.
The modified lysozyme spray generators 2 are provided with four sets, wherein two sets are respectively positioned at two sides of the flat ground at the edge of the culture wastewater pool 5 in the wastewater pool gas-collecting hood 1, and the other two sets are respectively positioned at the modified kaolin gel alkalinity absorption unit 3 and the HfOx/SiO 2 Outside of catalytic ozonation unit 4. Modified lysozymeAn ultrasonic system 14 and a modified lysozyme turbid liquid storage cavity 15 are arranged in the spray generator 2.
The modified kaolin gel alkaline absorption unit 3 is connected with the waste water pool gas-collecting hood 1 through a gas collecting main pipe 12. The gas collecting main pipe 12 is provided with an absorption unit electric valve 16 before entering the kaolin gel alkaline absorption unit 3; the gas collecting main pipe 12 is provided with a gas collecting bypass pipe 17 before being connected to the absorption unit electric valve 16, and the gas collecting bypass pipe 17 is provided with a bypass electric valve 18 and a vacuum pump 19. The two ends of the gas collecting bypass pipe 17 are connected with the gas collecting main pipe 12. The gas collecting main pipe 12 is finally connected into the modified kaolin gel alkaline absorption unit 3. The modified kaolin gel alkaline absorption unit 3 is internally filled with an organophosphonic acid modified kaolin gel 20 soaked in KOH solution. The top end inside the modified kaolin gel alkaline absorption unit 3 is provided with a first modified lysozyme spray header 21 and an alkaline absorption unit gas collection bell mouth 22. The first modified lysozyme spray shower head 21 is connected with the bacteroid peptide spray generator 2 outside the kaolin gel alkaline absorption unit 3. The gas collection bell mouth 22 of the alkaline absorption unit is connected with an exhaust pipe 23 of the alkaline absorption unit. The top of the modified kaolin gel alkaline absorption unit 3 is provided with a first pressure maintaining valve 24.
The HfOx/SiO 2 The catalytic ozonation unit 4 is connected to the modified kaolin gel alkalinity absorbing unit 3 through an alkalinity absorbing unit exhaust duct 23. A plurality of groups of HfOx/SiO are arranged inside the catalytic ozonation unit 4 2 And a catalyst 25. An ozone supply pipe 26 is introduced into the bottom of the catalytic ozonation unit 4, and the other end of the ozone supply pipe 26 is connected with an ozone generator 27. Second modified lysozyme spray shower head 28 and HfOx/SiO 2 The bacterial peptide spray generator 2 outside the catalytic ozone oxidation unit 4 is connected. The ozone oxidation gas collection bell mouth 29 is connected to an oxidation unit exhaust pipe 30. The oxidation unit exhaust pipe 30 penetrates out of the HfOx/SiO 2 The catalytic ozonation unit 4 is connected with an external air pump 31, HfOx/SiO 2 The top of the catalytic ozonation unit 4 is provided with a second pressure maintaining valve 32.
The device for killing the resistant microorganisms in the VOCs waste gas treatment system of the aquaculture wastewater pond is characterized in that the resistant microorganisms in each unit in the waste gas treatment system can be treated by the modified lysozyme spraying system 2 and the first modified lysozyme spraying 21 and the second modified lysozyme spraying spray header 28 in each unit, so that the killing work of each unit is independently carried out.
The modified lysozyme in the modified lysozyme turbid liquid storage cavity 15 is 1, 4-beta-N-lysozyme which is chemically modified by adopting a novel nonionic surfactant alkyl glycoside under the condition of far infrared radiation vibration. The preparation and chemical modification processes are as follows: preparing 0.01mmol/mL alkyl glycoside aqueous solution, slowly dripping 0.1mmol/mL alkyl glycoside aqueous solution into lysozyme solution (the mass concentration is about 50 mg/mL) under the condition of far infrared radiation (the wavelength is 4-14 microns), and continuously stirring for 20-40 min in the whole process. In this process, the far infrared radiation was intermittently performed for 5 seconds per minute. Finally obtaining a clear mixed solution of the alkyl glycoside and the lysozyme (the molar ratio is about 1: 8-1: 10). Centrifuging the mixed solution, washing off floating foam, and performing vacuum freeze drying to constant weight to obtain the novel modified lysozyme preparation. The process adopts the coupling of far infrared radiation and the surfactant, and utilizes the far infrared rays with specific wavelength to enable protein to generate resonance so as to improve the combination efficiency of the surfactant alkyl glycoside and the lysozyme, thereby improving the diffusion efficiency of the lysozyme in gas molecules and aerosol and the combination efficiency of the lysozyme and resistant microorganisms to be killed and killed, and strengthening the killing effect.
The invention provides a device for killing resistant microorganisms in a VOCs waste gas treatment system of a culture wastewater pond by utilizing the advantages of high efficiency, greenness, no resistance induction and the like of a modified lysozyme bactericide to solve the problem of ecological risks of the resistant microorganisms and corresponding resistant genes in the VOCs waste gas treatment system of the existing culture wastewater pond.
The working principle of the embodiment is as follows:
the device for killing resistant microorganisms in the VOCs waste gas treatment system of the aquaculture wastewater pond realizes the adsorption of VOCs, the removal of VOCs and the killing of the resistant microorganisms in the treatment system, and is respectively composed of a modified kaolin gel alkaline absorption unit and HfOx/SiO 2 A catalytic ozone oxidation unit and a modified lysozyme spray generator.Firstly, VOCs gas containing antibiotics is generated in a culture wastewater (aerobic) pool, the VOCs gas is collected through a gas-collecting bell mouth at the top of a gas-collecting hood of the wastewater pool, after the VOCs gas enters a modified kaolin gel alkaline absorption unit, a part of VOCs is absorbed by organic phosphonic acid modified kaolin gel soaked by KOH solution, and residual VOCs enter HfOx/SiO along with the gas 2 A catalytic ozonation unit. HfOx/SiO 2 Adsorbing VOCs to the surface area of the catalyst to increase the contact probability of ozone and organic matters; at the same time, HfOx/SiO 2 Catalytically activate ozone molecules, improve ozone decomposition generation, improve O, oxidize VOCs and remove odor. The cultivation wastewater pool usually contains a part of antibiotic and veterinary drug residues, which are easy to generate resistant microorganisms and accumulate in a waste gas treatment system, so the invention is provided with the modified lysozyme spray generator, and the atomized modified lysozyme solution small particles are used for respectively killing the resistant microorganisms in the structures such as the interior of a wastewater pool gas collecting hood, the interior of a kaolin gel alkaline absorption unit, the interior of a catalytic ozone oxidation unit, an auxiliary pipeline and the like. The modified lysozyme is chemically modified by adopting a novel nonionic surfactant alkyl glycoside under the condition of far infrared radiation vibration, and has better water solubility and fat solubility. In conclusion, the removal of VOCs and the disinfection of resistant microorganisms are realized by controlling specific operating conditions, such as kaolin gel concentration, ozone and catalyst content, particle size of modified lysozyme water atomized particles and the like, and the treatment of VOCs waste gas of aquaculture wastewater is realized on the whole.
The second embodiment is as follows:
the first difference between the present embodiment and the specific embodiment is: and closing the electric valve 16 of the absorption unit, opening the electric valve 18 of the bypass and the vacuum pump 19, and treating the VOCs waste gas in a vacuum pump suction mode, wherein the corresponding gel replacement frequency and the consumption rate of the modified lysozyme solution are doubled. The rest is the same as the first embodiment.
The third concrete implementation mode:
the embodiment utilizes the device for killing the resistant microorganisms in the VOCs waste gas treatment system of the aquaculture wastewater pond of the first embodiment and comprises the following steps:
firstly, an exhaust gas treatment stage:
the aquaculture wastewater usually contains antibiotics with higher concentration, under the condition that the aeration head 7 at the bottom of the wastewater treatment tank 5 provides oxygen, organic pollutants in the wastewater are degraded and metabolized, the water quality is purified, and a part of waste gas is generated; meanwhile, under the blowing-off action of the aeration head 7, VOCs gas containing antibiotics is dissipated to the upper part of the wastewater treatment tank 5 and the inside of the gas-collecting hood 1 of the wastewater treatment tank. The waste gas is collected through a plurality of gas collecting bell mouths 9, and then passes through the waste water pool gas collecting hood 1 through the gas collecting branch pipes 10 and the gas collecting main pipe 12 to enter the modified kaolin gel alkaline absorption unit 3. Carbon dioxide and most organic matters in the waste gas are absorbed by organic phosphonic acid modified kaolin gel KOH absorption liquid, and residual waste gas is collected through a gas collection bell mouth 22 of the alkaline absorption unit at the top and then enters HfOx/SiO through an exhaust pipe 23 of the alkaline absorption unit 2 A catalytic ozonation unit 4. The residual VOCs and small amounts of antibiotics in the exhaust gas are rapidly degraded and converted by the oxidation of ozone provided by the ozone generator 27 and the ozone supply line 26. The purified air is pumped by the external air pump 31.
Secondly, the killing stage of the resistant microorganisms in the exhaust system:
the wastewater treatment tank 5 was started up with the modified lysozyme spray generator 2 because of the presence of resistant microorganisms in all corners. The modified lysozyme turbid liquid storage cavity 15 in the modified lysozyme spray generator 2 generates water atomized liquid drops of 0.5-10 microns under the high-frequency vibration of the ultrasonic system 14. The modified lysozyme component is dispersed in the waste water pool gas-collecting hood 1, the modified kaolin gel alkaline absorption unit 3 and HfOx/SiO with water atomized liquid drops 2 The corners of the inner surface of the catalytic ozone oxidation unit 4 are catalyzed to achieve the aim of killing resistant microorganisms.
The fourth concrete implementation mode:
the first difference between the present embodiment and the specific embodiment is: step one, the vibration band frequency of an ultrasonic system 14 in the modified lysozyme spray generator 2 is 1.6-2.0M, the concentration of the modified lysozyme in the modified lysozyme suspension liquid storage cavity 15 is 5wt%, and the working temperature is 5-40 ℃.
The fifth concrete implementation mode:
the first difference between the present embodiment and the specific embodiment is: step one modified lysozyme spray generator 2 is discontinuous operation, and its operational mode is set for by operating technical personnel according to breeding the waste water treatment capacity, and under the general condition, the operating time ratio of waste water treatment pond (5) and modified lysozyme spray generator (2) is 24 h: 0.5 h.
The sixth specific implementation mode:
the first difference between the present embodiment and the specific embodiment is: step one, the modified kaolin gel alkaline absorption unit 3 contains 1wt% of KOH and 10wt% of organic phosphonic acid modified kaolin gel; the kaolin gel modified by organic phosphonic acid needs to be prepared in advance, the organic phosphonic acid is diethylenetriamine pentamethylene phosphonic acid, and the kaolin is modified in an NaOH alkaline environment; the gel replacement frequency is related to the waste gas treatment load, and generally, the gel solution loss is 1m per 1 ten thousand tons of aquaculture wastewater 3 。
The seventh embodiment:
the first difference between the present embodiment and the specific embodiment is: step one of the HfOx/SiO 2 The catalyst in the catalytic ozonation unit 4 is HfOx/SiO 2 Is prepared by self-assembling SiO 2 Growing the HfOx catalyst on the surface in situ; the catalyst loading was about 10%.
The specific implementation mode is eight:
the first difference between the present embodiment and the specific embodiment is: step one, the gas can process the waste gas by two modes of natural dissipation or vacuum pump suction: the absorption unit electric valve 16 is opened, the bypass electric valve 18 and the vacuum pump 19 are closed, and the waste gas can be treated by natural dissipation; the absorption unit electric valve 16 is closed, the bypass electric valve 18 and the vacuum pump 19 are opened, and the exhaust gas can be treated by the suction mode of the vacuum pump.
The following tests were used to verify the effect of the invention:
the waste gas treatment method for solving the problem that antibiotics contained in VOCs waste gas of the conventional aquaculture wastewater tank cause a large amount of resistant microorganisms in a treatment system comprises the following steps:
firstly, an exhaust gas treatment stage:
the flow rate of waste gas generated by the culture waste water (aerobic) pool 5 is 150-250 m 3 Min, VOCs concentration 1000mg/m 3 The temperature of the waste gas is 15-40 ℃, and the heavy peculiar smell exists. Waste gas is collected through a plurality of gas-collecting bell mouths at the top of a gas-collecting hood of the waste water tank, then passes through the gas-collecting hood of the waste water tank through a gas-collecting branch pipe and a gas-collecting main pipe, and enters a modified kaolin gel alkaline absorption unit 3, wherein the kaolin gel modified by organic phosphonic acid is immersed in a KOH solution, the mass fraction of the kaolin gel is 10%, and the mass fraction of the KOH is 1%; then the gas enters HfOx/SiO 2 Catalytic ozonation unit 4, catalyst HfOx/SiO 2 The filling ratio was about 10%, and the ozone concentration relative to the flow rate of the exhaust gas was about 1000mg/m 3 (ii) a The purified air is pumped by an external air pump, the ozone concentration is less than 0.5ppm, otherwise, reduction treatment is needed.
Secondly, the killing stage of the resistant microorganisms in the exhaust system:
a wastewater treatment tank 5, a modified kaolin gel alkaline absorption unit 3, HfOx/SiO 2 And detecting high relative abundance of the resistance genes at each sampling point in the catalytic ozonation unit 4. The modified lysozyme spray generator 2 is started, the mass concentration of the modified lysozyme solution in the modified lysozyme turbid liquid storage cavity 15 is 5%, and water atomized liquid drops of 0.05-10 micrometers are generated under the high-frequency (1.6-2.0 MHz) vibration of an ultrasonic system. The modified lysozyme component is dispersed in the gas-collecting hood of the wastewater tank, the modified kaolin gel alkaline absorption unit and the HfOx/SiO with the atomized water drops 2 Catalyzing each corner of the inner surface of the ozone oxidation unit to kill resistant microorganisms and reduce the ecological risk of resistant genes of the farm. The working temperature of the modified lysozyme generator is 5-40 ℃.
Compared with the common modified lysozyme (modified by only alkyl glycoside), the solubility of the modified lysozyme obtained in the method is respectively improved by 15 percent and 20 percent in a 5mM Tris-HCl (pH8.0) solution and a phosphate buffer solution with the pH =6.8, and the solubility of the modified lysozyme in an NaOH/sodium dodecyl sulfate organic solvent is improved by about 30 percent. According to the result of the 16sRNA quantitative analysis, the killing efficiency of the modified lysozyme disclosed by the invention on resistant microorganisms is improved by more than 10%.
The content of VOCs in the waste gas of the culture wastewater pond before and after treatment is detected by adopting 'environmental air volatile organic matter tank sampling/gas chromatography-mass spectrometry' (HJ 759), the removal rate of the VOCs is proved to be more than 95%, and the purified waste gas has no obvious odor. The method comprises the steps of carrying out 16S rRNA quantification and absolute quantification on the abundances of genes such as chloramphenicol resistance genes, sulfonamide resistance genes, tetracycline resistance genes and the like by adopting a standard plasmid external standard method, and finding that the copy number of the three resistance genes is 1.1-6.7 multiplied by 10 before and after the modified lysozyme is killed 9 copies·μL -1 Reduced to 1.2X 10 4 ~1.0×10 8 copies·μL -1 And the removal efficiency is more than 90%.
The specific modification scheme is as follows: preparing 0.01mmol/mL alkyl glycoside aqueous solution, slowly dripping 0.1mmol/mL alkyl glycoside aqueous solution into lysozyme solution (with mass concentration of about 50 mg/mL) under the condition of far infrared radiation (with the wavelength of 4-14 micrometers), and continuously stirring for 20-40 min in the whole process. In this process, the far infrared radiation was intermittently performed for 5 seconds per minute. Finally obtaining a clear mixed solution of the alkyl glycoside and the lysozyme (the molar ratio is about 1: 8-1: 10). Centrifuging the mixed solution, washing off froth, and performing vacuum freeze drying to constant weight to obtain the novel modified lysozyme preparation. The improved and synthesized process adopts the coupling of far infrared radiation and the surfactant, and utilizes the far infrared rays with specific wavelength to enable the protein to generate resonance so as to improve the combination efficiency of the surfactant alkyl glycoside and the lysozyme, thereby improving the diffusion efficiency of the lysozyme in gas molecules and aerosol and the combination efficiency of the lysozyme and resistant microorganisms to be killed and killed, and strengthening the killing and killing effect.
The mechanical modification and synthesis process adopts the coupling of far infrared radiation and a surfactant, and utilizes the far infrared rays with specific wavelength to enable protein to generate resonance so as to improve the combination efficiency of the surfactant alkyl glycoside and lysozyme, thereby improving the diffusion efficiency of the lysozyme in gas molecules and aerosol and the combination efficiency of the lysozyme and resistant microorganisms to be killed and killed, and strengthening the killing and killing effect.
Compared with the common modified lysozyme (only modified by alkyl glycoside), the mass transfer efficiency of the modified lysozyme obtained by the method is remarkably improved by 15-30%, the solubility of the modified lysozyme in a 5mM Tris-HCl (pH8.0) solution and a phosphate buffer solution with the pH =6.8 is respectively improved by 15% and 20%, and the solubility of the modified lysozyme in a NaOH/sodium dodecyl sulfate organic solvent is improved by about 30%. According to the result of 16sRNA quantitative analysis, the killing efficiency of the modified lysozyme on resistant microorganisms is improved by more than 10%.
(16 sRNA quantitative analysis procedures are very complicated, and are relatively conventional indicators for those skilled in the biological field, and are not described in detail.)
Compared with the common modified lysozyme (only modified by alkyl glycoside), the mass transfer efficiency of the modified lysozyme obtained by the method is remarkably improved by 15-30%, the solubility of the modified lysozyme in an organic phase and a water phase is respectively improved by 15% and 20% in a 5mM Tris-HCl (pH8.0) solution and a pH =6.8 phosphate buffer solution, and the solubility of the modified lysozyme in an NaOH/sodium dodecyl sulfate organic solvent is improved by about 30%. (the determination of solubility is relatively conventional and simple and is not described in detail.)
The waste gas produced in the treatment process in the aquaculture wastewater is rich in VOCs and antibiotics, so that the device has ideal treatment effect on the VOCs and the antibiotics. Other exhaust systems, such as medical facility exhaust, have low levels of VOCs and the types of drugs used in medical facilities are complex and certain components may affect lysozyme activity. Therefore, the current experimental data show that the treatment effect of the technology on the waste gas generated by the culture wastewater treatment is optimal. The experimental data are as follows:
the device is adopted to treat the waste gas of the culture wastewater tank or the aeration tank, the removal rate of VOCs before and after treatment is more than 95 percent, and the purified waste gas has no odor. The method comprises the steps of quantifying 16S rRNA, absolutely quantifying the abundance of genes such as chloramphenicol resistance genes, sulfonamide resistance genes and tetracycline resistance genes by adopting a standard plasmid external standard method, and finding that the copy number of the three resistance genes is 1.1-6.7 multiplied by 10 before and after the modified lysozyme is killed 9 copies·μL -1 Reduced to 1.5X 10 3 ~2.0×10 7 copies·μL -1 And the removal efficiency is more than 99%.
(II) Hospital machine treated by the deviceWaste gas generated in the sewage treatment process is formed, and the removal rate of VOCs before and after treatment is more than 80%. The results of the quantitative analysis of 16S rRNA show that the copy number of the chloramphenicol resistance gene, the sulfonamide resistance gene and the tetracycline resistance gene is 4.0-8.0 multiplied by 10 10 copies·μL -1 Reduced to 7.5X 10 8 ~8.0×10 9 copies·μL -1 And the removal efficiency is more than 90%.

Claims (8)

1. A kind of sterilizing agent, characterized by that this sterilizing agent is to the modification and synthesis of lysozyme, adopt the coupling of far infrared radiation and surfactant active, make lysozyme produce resonance under far infrared radiation condition, impel the combination of surfactant active and lysozyme, the combined state of the two can raise the diffusion efficiency of lysozyme in gas molecule, aerosol, and lysozyme and wait to sterilize the combination efficiency of resistant microorganism; the modification and synthesis process of the lysozyme is used for obtaining the modified lysozyme reinforced disinfectant;
the surfactant is alkyl glycoside surfactant;
the preparation method of the modified lysozyme reinforced disinfectant comprises the following steps: preparing 0.01mmol/mL alkyl glycoside aqueous solution, slowly dripping 0.1mmol/mL alkyl glycoside aqueous solution into 50mg/mL lysozyme solution under the condition of far infrared radiation with the wavelength of 4-14 microns, and continuously stirring for 20-40 min in the whole process; in the process, far infrared radiation is carried out intermittently, and the radiation time per minute is 5 s; finally obtaining a clear mixed solution with the molar ratio of the alkyl glycoside to the lysozyme being 1: 8-1: 10; centrifuging the mixed solution, washing off floating foam, and freeze-drying in vacuum to constant weight to obtain the modified lysozyme reinforced disinfectant.
2. A system and method for treating VOCs waste gas in a culture wastewater pond is characterized by comprising the following steps: aiming at VOCs waste gas in a culture wastewater pond, in particular to resistant microorganisms in the waste gas, the sterilizing agent disclosed by claim 1 is utilized to generate micron-sized modified lysozyme spray under ultrasonic vibration to sterilize the waste gas, in particular to efficiently sterilize the resistant microorganisms in the waste gas, so that the sterilizing breadth and the sterilizing efficiency of the resistant microorganisms in a waste gas system can be improved, the content of the resistant microorganisms contained in waste gas aerosol is reduced, and the resistance cannot be induced in the waste gas; and the exhaust gas is treated by combining the triple processes of modified lysozyme, modified kaolin gel and catalytic ozonation, so that the exhaust emission quality is improved.
3. The method for treating VOCs waste gas in a culture wastewater pond according to claim 2, wherein the method comprises the following steps: a wastewater pool gas-collecting hood is additionally arranged above the breeding wastewater pool, a modified lysozyme ultrasonic spraying device is arranged in the hood, waste gas generated by wastewater is subjected to sterilization treatment, the sterilized waste gas is collected above the wastewater pool gas-collecting hood and is dredged into a modified kaolin gel alkaline absorption unit to perform alkaline absorption on the waste gas, and the modified lysozyme ultrasonic spraying is used for performing sterilization treatment on the waste gas in the unit in the absorption process; the unit waste gas is dredged to HfOx/SiO 2 The catalytic ozone oxidation unit is used for carrying out catalytic ozone oxidation treatment on the waste gas in the unit, and the waste gas in the unit is subjected to sterilization treatment by ultrasonic spraying of modified lysozyme in the oxidation process; and finally, discharging the waste water out of the environment.
4. The utility model provides a breed effluent disposal system device of pond VOCs exhaust-gas treatment which characterized in that: the system device comprises: a gas-collecting hood (1) of the wastewater pool, a modified lysozyme spray generator (2), a modified kaolin gel alkaline absorption unit (3), HfOx/SiO 2 A catalytic ozonation unit (4);
an aeration pipeline (6) is arranged at the bottom of the culture wastewater pool (5), aeration heads (7) are distributed on the pipe body of the aeration pipeline (6), and the upstream of the aeration pipeline (6) is connected with an air blower (8) outside the pool;
an aeration system in the culture wastewater tank (5) is formed by the blower (8), the aeration pipeline (6) and the aeration head (7);
a sealed cover above the mouth of the breeding wastewater pool (5) is buckled with a wastewater pool gas-collecting hood (1); the waste water pool gas-collecting hood (1) is provided with a bulge which is arched upwards, and the space in the hood of the waste water pool gas-collecting hood (1) and the space above the waste water liquid level of the breeding waste water pool (5) form a waste gas treatment space;
modified lysozyme spray generators (2) are arranged between the peripheries of the pool openings of the culture wastewater pools (5) of the wastewater pool gas-collecting hood (1), and the modified lysozyme spray generators (2) are distributed in pairs in opposite directions; an ultrasonic system (14) and a modified lysozyme turbid liquid storage cavity (15) are arranged in the modified lysozyme spray generator (2); the modified lysozyme turbid liquid storage cavity (15) is filled with the disinfectant as claimed in claim 1, and an ultrasonic system (14) of the modified lysozyme spray generator (2) covers an exhaust gas treatment space;
a plurality of gas collection bellmouths (9) are arranged in a dome of a gas collection hood (1) of the wastewater pool, the gas collection bellmouths (9) are converged and communicated to a gas collection main pipe (12) through gas collection branch pipes (10), and the gas collection main pipe (12) extends and is communicated to the bottom space of an inner cavity of a modified kaolin gel alkaline absorption unit (3) outside the gas collection hood (1) of the wastewater pool;
the middle layer of the inner cavity of the modified kaolin gel alkaline absorption unit (3) is filled with organic phosphonic acid modified kaolin gel (20) soaked by KOH solution;
the first modified lysozyme spray header (21) is arranged at the top of the inner cavity of the modified kaolin gel alkaline absorption unit (3);
the filler space of the organic phosphonic acid modified kaolin gel (20) soaked by the KOH solution forms a filler mass transfer and sterilization channel of cross flow spraying of the alkaline absorption unit;
the top layer of the inner cavity of the modified kaolin gel alkaline absorption unit (3) is provided with an alkaline absorption unit gas collection bell mouth (22), and the alkaline absorption unit gas collection bell mouth (22) is communicated to HfOx/SiO through an alkaline absorption unit exhaust pipe (23) 2 A bottom cavity of the catalytic ozone oxidation unit (4);
HfOx/SiO 2 a plurality of groups of HfOx/SiO are uniformly and fixedly distributed in the inner cavity of the catalytic ozonation unit (4) 2 A catalyst (25) suspension;
an ozone supply pipe (26) of the ozone generator (27) is communicated with HfOx/SiO 2 A bottom cavity of the catalytic ozone oxidation unit (4);
HfOx/SiO 2 the top of the inner cavity of the catalytic ozone oxidation unit (4) is provided with a second modified lysozyme spray header (28);
multi-group HfOx/SiO 2 The catalyst (25) suspension space forms a mass transfer oxidation killing channel of cross-flow spraying of the ozone oxidation unit;
HfOx/SiO 2 an ozone oxidation gas collection bell mouth (29) is arranged in the top space of the inner cavity of the catalytic ozone oxidation unit (4), the ozone oxidation gas collection bell mouth (29) is connected with an external air pump (31) through an oxidation unit exhaust pipe (30), and the air pump (31) exhausts air to the outside.
5. The waste gas treatment system device for VOCs in aquaculture wastewater pond of claim 4, wherein the waste gas treatment process of the system device is as follows:
under the condition that an aeration head (7) at the bottom of a culture wastewater pool (5) provides oxygen, organic pollutants in wastewater are degraded and metabolized, the water quality of the wastewater is purified, and a part of waste gas is generated; meanwhile, under the blowing-off action of the aeration head (7), VOCs waste gas containing antibiotics is dissipated to the upper part of the waste water treatment tank (5) and the inside of the waste water tank gas-collecting hood (1);
waste gas is collected through a plurality of gas-collecting bell mouths (9), and then passes through a gas-collecting branch pipe (10) and a gas-collecting main pipe (12) to penetrate out of a waste water tank gas-collecting hood (1) and enter a modified kaolin gel alkaline absorption unit (3);
carbon dioxide and most organic matters in the waste gas are absorbed by organic phosphonic acid modified kaolin gel KOH absorption liquid, and residual waste gas enters HfOx/SiO through an alkaline absorption unit exhaust pipe (23) after being collected through a gas collection bell mouth (22) of the alkaline absorption unit at the top 2 A catalytic ozonation unit (4);
HfOx/SiO 2 residual VOCs and a small amount of antibiotics in the waste gas in the catalytic ozone oxidation unit (4) are quickly degraded and converted under the oxidation action of ozone provided by an ozone generator (27) and an ozone supply pipe (26); the purified air is pumped away by an external air pump (31);
the killing process of the system device parallel to the waste gas treatment process is as follows:
the modified lysozyme suspension storage cavity (15) in the modified lysozyme spray generator (2) generates water atomized liquid drops of 0.5-10 microns under the high-frequency vibration of the ultrasonic system (14); the modified lysozyme component is dispersed in the wastewater pool gas-collecting hood (1), the modified kaolin gel alkalinity absorption unit (3) and HfOx/SiO with water atomized liquid drops 2 The corners of the space and the inner surface in the catalytic ozone oxidation unit (4) achieve the aim of killing resistant microorganisms;
and the water atomized liquid drops of the modified lysozyme are dropped in the space of the waste water pool gas collecting hood (1), the space of the modified kaolin gel alkalinity absorption unit (3), HfOx/SiO 2 The space in the catalytic ozone oxidation unit (4) forms stepwise killing of the waste gas treatment process.
6. The waste gas treatment system device for VOCs in the aquaculture wastewater pond of claim 4, wherein: the vibration band frequency of an ultrasonic system (14) in the modified lysozyme spray generator (2) is 1.6-2.0 MHz, the concentration of modified lysozyme in the modified lysozyme suspension storage cavity (15) is 5wt%, and the working temperature is 5-40 ℃;
modified lysozyme spray generator (2) is discontinuous operation, and its operational mode is set for according to breeding the waste water treatment capacity by operating technical personnel, and under the general condition, the operating time ratio of waste water treatment pond (5) and modified lysozyme spray generator (2) is 24 h: 0.5 h;
the modified kaolin gel alkaline absorption unit (3) contains 1wt% of KOH and 10wt% of organic phosphonic acid modified kaolin gel; the kaolin gel modified by organic phosphonic acid needs to be prepared in advance, the organic phosphonic acid is diethylenetriamine pentamethylene phosphonic acid, and the kaolin is modified in an NaOH alkaline environment;
HfOx/SiO 2 the catalyst in the catalytic ozone oxidation unit (4) is HfOx/SiO 2 Is prepared by self-assembling SiO 2 Growing HfOx catalyst on the surface in situ; catalyst packingThe charging rate was 10%.
7. Use of a biocide according to claim 1 in a process for the biocidal treatment of exhaust gases.
8. The use of the system and method for treating VOCs in aquaculture wastewater ponds according to claim 2 or 3 in waste gas disinfection treatment processes.
CN202210939431.9A 2022-08-05 2022-08-05 System method and device for treating VOCs waste gas in disinfectant and aquaculture wastewater pool Active CN114984746B (en)

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