CN112933965A - Green and efficient ship waste gas multi-pollutant purification system and intelligent regulation and control method - Google Patents
Green and efficient ship waste gas multi-pollutant purification system and intelligent regulation and control method Download PDFInfo
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- B01D53/48—Sulfur compounds
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- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
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Abstract
The invention relates to a green and efficient ship waste gas multi-pollutant removal and purification system and an intelligent regulation and control method, wherein the system comprises a device part, a sensing part, a control part and an optimization part, wherein the device part comprises a ship diesel engine, a multi-pollutant detergent preparation device, a multi-pollutant enhanced removal device, a multi-pollutant washing residual liquid integrated purification device and a waste gas exhaust funnel; the sensing part is used for acquiring, preprocessing, integrating, storing and issuing information; the control part adjusts key operation quantity through real-time operation working conditions and optimization parameter setting, and ensures that the system stably reaches the standard and is optimally adjusted; the optimization part comprises a calculation platform constructed by a pollutant generation concentration and outlet pollutant concentration prediction model, intelligent switching of a desulfurization operation mode under frequent change of navigation environment and frequent fluctuation of load is realized, accurate adjustment and optimized regulation of system operation key parameters are realized, energy is saved, consumption is reduced, emission stability is improved, and environmental pollutants and resource consumption are reduced.
Description
Technical Field
The invention belongs to the technical field of ships, and particularly relates to a green and efficient ship waste gas multi-pollutant purification system and an intelligent regulation and control method.
Background
With the gradual increase of international trade, the ship transportation industry is also rapidly developed. But at the same time, the problem of environmental pollution caused by the exhaust gas of ships burning petroleum products is also becoming more serious. Heavy oil is mostly used as fuel in large ocean vessels, the sulfur content of the heavy oil can reach more than 3.5%, and sulfur oxides (SOx) in waste gas have great influence on the environment. In order to reduce the environmental pollution caused by ships, the modification about the reduction of the sulfur oxide emission of ships is clearly required by the 58 th meeting of the Maritime Environmental Protection Committee (MEPC) passing the MARPOL73/78 convention VI: the sulfur content of the fuel oil can not exceed 0.1% (m/m) in a sulfur oxide (SOx) emission control area from 1 month and 1 day 2015, and the sulfur content of the fuel oil can not exceed 0.5% (m/m) outside the sulfur oxide (SOx) emission control area from 1 month and 1 day 2020. The International Maritime Organization (IMO) Maritime Environmental Protection Commission (MEPC) stipulates that ships not equipped with a desulfurization unit from the date of the coming into effect of the regulations are prohibited from carrying fuel oil with an overproof sulfur content.
Currently, there are two approaches to achieving sulfur emission targets: the method is characterized in that low-sulfur oil or alternative fuel is used, and a ship flue gas desulfurization device is additionally arranged. The use of low sulfur oil or alternative fuels is costly and requires corresponding technical modifications to the ship's fuel equipment. Therefore, the additional installation of the ship flue gas desulfurization device is used for controlling the SO of the ship2One of the important measures for emissions.
The ship waste gas wet desulfurization system mainly has three technical forms: firstly, an open desulfurization system uses seawater as an absorbent, the seawater is alkalescent and can absorb SOx in discharged flue gas to generate sulfite, and the reacted seawater is treated by aeration and the like and is discharged into the sea after meeting the standard; secondly, adding alkaline absorbents such as sodium hydroxide or magnesium hydroxide slurry into circulating water to absorb SOx in the discharged flue gas in a closed system, and performing neutralization reaction to generate sulfite and water; the mixed desulfurization system combines the starting system and the closed system together, and can freely switch between the open system and the closed system. The open type ship desulfurization technology directly introduces seawater to participate in reaction and then discharges the seawater to the sea, so that the open type ship desulfurization technology has higher requirements on application sea areas, simultaneously, many countries around the world have discharge prohibition on offshore sea areas, and the recent publication of '2020 global ship fuel oil sulfur limit regulation implementation scheme' formulated by the China maritime work bureau requires that the washing water of the open type waste cleaning system cannot be discharged in the ship atmospheric pollutant discharge control area in China.
The low-cost stable sulfur dioxide standard emission realization of the existing ship tail gas desulfurization system faces the following challenges: firstly, sulfur dioxide is difficult to stably reach the standard and discharge when oil products with high sulfur content are combusted, and meanwhile, the cost of using low-sulfur oil or replacing fuel is higher, and corresponding technical transformation is needed to be carried out on ship fuel oil equipment; secondly, the low-cost and high-efficiency ship tail gas desulfurization is realized under the conditions of small available space on the ship, small storage amount of the desulfurization absorbent and byproducts and the like; in the process of sailing on the sea, the phenomenon of ship body vibration, swinging and the like can cause the desulfurizing tower to incline to a certain degree, so that the distribution nonuniformity of gas and liquid in the tower is increased, the fluctuation range of the desulfurizing efficiency of the desulfurizing tower is large, and the desulfurizing efficiency sometimes exceeds the standard; fourthly, the contents of heavy metal ions, PAH, carbon black and other fine particles in the ship desulfurization washing residual liquid are high, and meanwhile, in order to prevent the pollution of the washing residual liquid to the ocean, the ocean environmental protection Committee (MEPC) makes strict regulations on the discharge of the washing residual liquid of the ship exhaust gas washing desulfurization equipment, and the discharge requirement is high, so that the post-treatment difficulty is high; the selection and operation of the mixed mode are mainly carried out according to manual judgment, the influence of marine operation environment of the ship, such as seawater temperature, alkalinity, ship shaking and other adverse conditions, cannot be fully considered by the adjustment of the control system, and advanced prediction cannot be carried out, SO that SO (SO) is caused2The emission does not reach the standard, the operation energy consumption is large, and the operation intensity of the crew is high.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a green and efficient ship waste gas multi-pollutant purification system and an intelligent regulation and control method, which solve the problem of SO caused by burning inferior oil products in a complex navigation environment of a ship at low cost and high efficiency2The problem of standard exceeding of emission is solved, and the adaptability of the ship to complex working conditions in the running process is improved; method for realizing open-loop and closed-loop desulfurization modes by simultaneously utilizing intelligent regulation and control methodIntelligent switching, reduced SO2The discharge fluctuation saves the material consumption and the power consumption of alkali liquor, fresh water and the like, and further reduces the operating intensity of crew, and the like; meanwhile, the ship desulfurization washing water post-treatment system which is environment-friendly, energy-saving, efficient and compact is developed by combining the standby points of limited installation space, limited reaction time and small treated water amount in the ship environment, and the problems of limited ship desulfurization waste water post-treatment space, high emission requirement and the like are solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
a green and high-efficiency ship exhaust gas multi-pollutant removal and purification system comprises a device part, a sensing part, a control part and an optimization part,
the device part comprises a marine diesel engine, a multi-pollutant detergent preparation device, a multi-pollutant reinforced removal device, a multi-pollutant washing residual liquid integrated purification device and an exhaust gas exhaust funnel, and sulfur dioxide is absorbed and removed and heavy metal ions, PAH, carbon black and other fine particles are washed and removed through physical and chemical reactions;
the sensing part comprises an instrument for acquiring various data and a processor for analyzing the data, and information acquisition, preprocessing, integration, storage and distribution are carried out through an instrument on-line detection device and other sensing and communication equipment;
the control part comprises a valve, a pump and other linkage control devices, and key operation quantity adjustment is carried out through real-time operation working conditions and optimized parameter setting, so that the system is ensured to be stable and reach the standard and optimized and adjusted;
the optimization part comprises a calculation platform constructed by a pollutant generation concentration and outlet pollutant concentration prediction model, intelligent switching of a desulfurization operation mode under frequent change of navigation environment and frequent fluctuation of load is realized, accurate adjustment and optimized regulation of key parameters of system operation are realized, energy is saved, consumption is reduced, emission stability is improved, and environmental pollutants and resource consumption are reduced.
Preferably, the multi-pollutant detergent preparation device comprises a multi-pollutant detergent circulation tank, a seawater or fresh water extraction pump, a multi-pollutant detergent activity adding device and a multi-pollutant detergent metering and controlling device, wherein an alkali liquor is arranged in the multi-pollutant detergent activity adding device, the multi-pollutant detergent circulation tank is respectively connected with the seawater or fresh water extraction pump, the multi-pollutant detergent activity adding device and the multi-pollutant detergent metering and controlling device, and a multi-pollutant detergent delivery pump is arranged on a pipeline connecting the multi-pollutant detergent circulation tank and the multi-pollutant detergent metering and controlling device;
when the requirement on the emission limit value of low-sulfur product oil or sulfur dioxide for combustion of ships is not high, the seawater or fresh water extraction pump pumps seawater to the multi-pollutant detergent circulation tank, and the multi-pollutant detergent delivery pump is used for delivering the seawater to the multi-pollutant enhanced removal device for washing and removing sulfur dioxide and washing and removing fine particles such as heavy metal ions, PAH (polycyclic aromatic hydrocarbon), carbon black and the like; further, when the emission limit of the high-sulfur oil for ship combustion or sulfur dioxide is strictly required, the multi-pollutant detergent activity adding device adds alkali liquor (such as magnesium hydroxide slurry) to the multi-pollutant detergent circulating tank to realize deep removal of fine particles such as sulfur dioxide, heavy metal ions, PAH and carbon black; the multi-pollutant detergent metering and regulating device can regulate and record the consumption of the multi-pollutant detergent in real time;
the multi-pollutant washing agent metering and regulating device is communicated with the lower part of the multi-pollutant absorption tower;
the removal of fine particles such as sulfur dioxide, heavy metal ions, PAH, carbon black and the like is enhanced by coupling mass transfer and reaction processes of migration/removal of different pollutants in different scale spaces through gas-gas/gas-solid mixing, particle-liquid drop mutual collision, gas-liquid/gas-liquid-solid mass transfer and in-phase complex chemical reaction in a reaction space of the multi-pollutant absorption tower; the dense-phase enhanced mass transfer absorption area has strong mass transfer by constructing a mass transfer effect in the multi-pollutant absorption towerThe dense phase zone has the advantages of strong mixing, large specific surface area and the like, and obviously increases SO2The desulfurization efficiency of the concentration flue gas; the multi-pollutant detergent spraying device is connected with the detergent variable-frequency circulating pump, and the detergent variable-frequency circulating pump is connected with the multi-pollutant detergent circulating tank; the multi-pollutant detergent spraying device can control parameters such as liquid-gas ratio, temperature, pH value and the like of detergent solution in the multi-pollutant absorption tower in real time to strengthen SO2Absorbing and trapping heavy metal ions, PAH, carbon black and other fine particles;
the integrated purification device for the pollutant washing residual liquid comprises a washing residual liquid buffer tank, a detergent residual liquid storage tank, an aeration tank, a centrifugal separator, a high-voltage pulse corona reactor and a water quality adjusting tank which are sequentially communicated, wherein the water quality adjusting tank is communicated with the washing residual liquid buffer tank; the bottom of the absorption tower is communicated with a washing raffinate buffer tank through a washing raffinate discharge pump, the washing raffinate buffer tank is communicated with a washing raffinate storage tank through a first washing raffinate delivery pump, a flocculating and sequestering agent adding port is arranged on the washing raffinate storage tank, the raffinate storage tank is communicated with an aeration tank through a second washing raffinate delivery pump, the aeration tank is connected with aeration equipment, a centrifugal separator is connected with a filter press, and the filter press is connected with a filter residue barrel;
adding a chelating agent into the washing residual liquid buffer tank to flocculate heavy metal ions captured by the multi-pollutant enhanced removal device, then introducing the washing residual liquid into the aeration tank for aeration, introducing the washing residual liquid into the centrifugal separator after sufficient oxidation to separate particles and flocculated precipitates, introducing the particles such as carbon black in the washing liquid into the centrifugal separator to separate particles with the particle size of 30-40 mu m, and then adding an aggregating agent and a flocculating agent into the residual liquid to aggregate and precipitate unseparated fine particles (the separated residues are stored by a special storage tank to be discharged to the bank); solid impurity process get into behind the pressure filter the sediment bucket, the washing liquid after the filtration gets into afterwards high-voltage pulse corona reactor degradation PAHs, process washing liquid after the quality of water equalizing basin is adjusted detects emission after up to standard.
Preferably, in the multi-pollutant detergent preparation device, seawater is used as a detergent, the pH value of a detergent solution is controlled to be 7.5-8.3, and the total alkalinity is 2.0-3.0 mmol/L; the alkali liquor is magnesium hydroxide slurry, the magnesium hydroxide slurry is used as a detergent, the pH value of a detergent solution is controlled to be 5.0-6.5, and the molar ratio of magnesium to sulfur is not more than 1.05;
in the multi-pollutant reinforced removing device, seawater is used as a washing agent, and SO is reinforced by additionally arranging a dense phase region and increasing pH2Absorbing and removing heavy metal ions, PAH carbon black and other fine particles; magnesium hydroxide slurry is used as a washing agent, and SO is strengthened by adjusting liquid-gas ratio and adding a dense-phase region2Absorption and removal of heavy metal ions, PAH, carbon black and other fine particles;
seawater is used as a detergent, and the liquid-gas ratio of the detergent solution is not less than 10L/Nm3Controlling the temperature to be 15-30 ℃; the magnesium hydroxide slurry is used as a detergent, and the liquid-gas ratio of the detergent solution is more than 5L/Nm3And controlling the temperature to be 40-52 ℃.
Preferably, the nozzles at the bottommost layer of the multi-pollutant detergent spraying device are provided with one-way solid cone nozzles, and the rest are provided with two-way solid cone nozzles.
The oil substances and Polycyclic Aromatic Hydrocarbons (PAHs) which are not completely combusted in the washing liquid are degraded by a high-voltage pulse corona method. Preferably, the pulse frequency of the high-voltage pulse power supply is 180Hz, the pulse voltage is 42kV, and the aeration is O2The volume flow of the treatment solution is 6L/min, the pH value is controlled to be 5.5-6.0, and the treatment time is 120 min.
The invention also provides an intelligent regulation and control method of the green and efficient ship waste gas multi-pollutant removal and purification system, which comprises the following steps:
(1) the sensing part collects key operation and design parameters of the ship and the ship waste gas multi-pollutant removal and purification system through arranged instruments and sensors;
(2) the optimization part collects key operation and design parameters of the ship and ship waste gas multi-pollutant removal and purification system through the sensing part to construct a multi-dimensional database and establish a multi-pollutant concentration generation-removal prediction model;
(3) based on the model, the pollutant emission data under the current working condition is predicted in advance, the control part is utilized to realize the switching of the multi-pollutant detergent in advance, and the key operation parameters of the multi-pollutant enhanced removal device are adjusted to be accurately adjusted and optimally regulated.
Preferably, the key operation and design parameters in step (1) include ship information including ship sailing position, speed, and ship swing, diesel engine operation load, exhaust emission from diesel engine outlet, exhaust pollutant concentration, exhaust temperature, exhaust pressure, seawater temperature, seawater pH, seawater base number, multi-pollutant detergent consumption, pH, temperature, detergent spraying amount, pulse frequency, pulse voltage, and aeration O of high-voltage pulse power supply2Volume flow, pH value of aeration tank and aeration treatment time.
The sensing part collects ship information such as ship sailing position, sailing speed, ship body swing and the like through sensors such as instruments and meters arranged on a ship and a ship waste gas multi-pollutant removal and purification system, data such as diesel engine operation load, diesel engine outlet waste gas discharge amount, waste gas pollutant concentration, waste gas temperature, pressure and the like, seawater parameters such as seawater temperature, pH value, alkali value and the like, key operation and design parameters of a multi-pollutant enhanced removal device such as multi-pollutant detergent consumption, pH, temperature, detergent spraying amount and the like, pulse frequency, pulse voltage and aeration O of a high-voltage pulse power supply2The volume flow, the pH value of the aeration tank, the aeration treatment time and other key operation parameters of the integrated purification device for the washing residual liquid of the pollutants.
The optimization part collects key operation and design data of the ship and the ship waste gas multi-pollutant removal and purification system through the sensing part to construct a multi-dimensional database, and a prediction model of the generation concentration of the multi-pollutants at the side of the diesel engine, the outlet temperature and the like is established aiming at the problem that the measurement of the concentration of the pollutants at the inlet of the multi-pollutant enhanced removal device is lagged or inaccurate due to the complex and changeable navigation working conditions. Further based on the process characteristics of generating and removing the multiple pollutants in the ship exhaust gas, determining key factors influencing the generation and removal of the pollutants, establishing a multiple pollutant concentration generation-removal prediction model, and realizing the accurate prediction of the multiple section pollutant concentration.
Preferably, the establishment of the multi-pollutant concentration generation-removal prediction model specifically comprises the following steps:
s1: collecting key operation and design parameters of the ship and the ship waste gas multi-pollutant removal and purification system collected by the sensing part, and establishing a multi-dimensional database covering key parameters of ship waste gas pollutant emission reduction system design, operation, energy consumption and material consumption;
s2: establishing a diesel engine side SO through the diesel engine side including load, combustion air supply quantity, temperature and oxygen quantity key parameters2Generating a concentration prediction model;
s3: SO removal device based on multiple pollutants2Mechanism, respectively establishes that seawater and alkali liquid absorbent are used as detergents to remove SO2By utilizing the historical data correction model, the seawater and alkali liquor absorption liquid method desulfurization inlet SO are respectively obtained2Concentration, temperature, detergent spraying amount, slurry density, pH value, ship inclination angle, navigation area and multi-pollutant removal device outlet SO2The corresponding relation of concentration;
s4: meanwhile, further utilizing historical operation data and test data and utilizing a data modeling method to respectively obtain corresponding relations between the concentration of particles at the inlet of the seawater and alkali liquor absorbent desulfurization process, the temperature of inlet waste gas, the spraying amount of a washing agent, the density of slurry, the pH value, the inclination angle of a ship, the concentration of particles at the outlet of the multi-pollutant removal device and polycyclic aromatic hydrocarbon;
s5: based on the corresponding relation, the deep neural network and the random forest data model are trained by utilizing the prediction deviation of the correction model on the basis, the prediction precision and the generalization capability of the model are further improved, a multi-pollutant concentration generation-removal prediction model is established, and the accurate prediction of the multi-section pollutant concentration is realized.
Preferably, the diesel side SO2The concentration prediction model was generated as follows:
Y＝f(X,V0,T,S,β,ɑ)
wherein Y is the side SO of diesel engine2Formation concentration, X is load, V0Theoretical amount of air for combustionT is the boiler side temperature, S is the fuel sulfur content, alpha is the excess air coefficient, and beta is the incomplete combustion loss of the diesel engine machinery.
Preferably, the outlet SO of the multi-pollutant reinforced removal device2The concentration prediction model is as follows:
W＝f(Y,Q,T1,ρ,I,Θ)
in the formula, W is the outlet SO of the multi-pollutant reinforced removal device2Concentration, Y is side SO of diesel engine2The concentration of the product, Q detergent spray amount, rho is the slurry density, I is the pH value, T1And theta is the ship inclination angle for the inlet side temperature of the multi-pollutant reinforced removal device.
And optimizing a pollutant concentration prediction model established by the part to realize the advanced prediction of pollutant emission data under the current working condition, and utilizing a control system to realize the switching of the multi-pollutant detergent in advance, namely adopting seawater or magnesium hydroxide as an absorption detergent, and adjusting the key operation parameters of the multi-pollutant enhanced removal device to accurately adjust, optimize and regulate, so as to realize the automatic start and stop of key equipment, further realize the purposes of saving energy, reducing consumption, improving emission stability and reducing the consumption of environmental pollutants and resources.
Compared with the prior art, the invention has the beneficial effects that:
the invention solves the problem of SO caused by burning inferior oil products in the complex navigation environment of the ship with low cost and high efficiency2The problem of standard exceeding of emission is solved, and the adaptability of the ship to complex working conditions in the running process is improved; meanwhile, the intelligent switching between open-loop and closed-loop desulfurization modes is realized by using an intelligent regulation and control method, SO that SO (sulfur oxide) is reduced2The discharge fluctuation saves the material consumption and the power consumption of alkali liquor, fresh water and the like, and further reduces the operating intensity of crew, and the like; meanwhile, the ship desulfurization washing water post-treatment system which is environment-friendly, energy-saving, efficient and compact is developed by combining the standby points of limited installation space, limited reaction time and small treated water amount in the ship environment, and the problems of limited ship desulfurization waste water post-treatment space, high emission requirement and the like are solved.
Drawings
FIG. 1 is a frame diagram of the intelligent regulation and control system for removing and purifying multiple pollutants from the exhaust gas of a green and efficient ship;
FIG. 2 is a flow chart of the green and efficient system for removing and purifying multiple pollutants from ship exhaust gas according to the present invention;
FIG. 3 is a schematic view of the construction of the multi-pollutant detergent preparing apparatus according to the present invention;
FIG. 4 is a schematic structural diagram of an enhanced multi-pollutant removal device according to the present invention;
FIG. 5 is a schematic structural diagram of the integrated purification device for the contaminant washing residual liquid of the present invention.
Detailed Description
The invention is further illustrated with reference to specific examples, without however being limited thereto. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the protection scope of the present invention.
Example 1
With reference to figure 1 of the drawings,
a green and high-efficiency ship exhaust gas multi-pollutant removal and purification system comprises a device part, a sensing part, a control part and an optimization part,
the device comprises a marine diesel engine 1, a multi-pollutant detergent preparation device 2, a multi-pollutant enhanced removal device 3, a multi-pollutant washing residual liquid integrated purification device 4 and a waste gas exhaust funnel 5, and is characterized in that a series of physical and chemical reactions are used for absorbing and removing sulfur dioxide, washing and removing heavy metal ions, PAH, carbon black and other fine particles;
the sensing part comprises devices such as instruments and meters for acquiring various data, a processor for analyzing the data and the like, and information acquisition, pretreatment, integration, storage and distribution are carried out through an instrument and meter online detection device and other sensing and communication equipment;
the control part comprises linkage control devices such as valves and pumps and the like which are positioned in the multi-pollutant detergent preparation device 2, the multi-pollutant enhanced removal device 3 and the multi-pollutant washing residual liquid integrated purification device 4, and key operation quantity adjustment is carried out, and the system is ensured to stably reach the standard and be optimally adjusted through real-time operation working condition and optimized parameter setting;
the optimization part comprises a calculation platform constructed by a pollutant generation concentration and outlet pollutant concentration prediction model, intelligent switching of a desulfurization operation mode under frequent change of navigation environment and frequent fluctuation of load is realized, accurate adjustment and optimized regulation of key parameters of system operation are realized, energy is saved, consumption is reduced, emission stability is improved, and environmental pollutants and resource consumption are reduced.
Referring to fig. 2 to 5, the multi-pollutant detergent preparation device 2 includes a multi-pollutant detergent circulation tank 22, a seawater or fresh water extraction pump 21, a multi-pollutant detergent activity adding device 23, and a multi-pollutant detergent metering and controlling device 25, wherein an alkali solution (such as magnesium hydroxide slurry) is disposed in the multi-pollutant detergent activity adding device 23, the multi-pollutant detergent circulation tank 22 is respectively connected with the seawater or fresh water extraction pump 21, the multi-pollutant detergent activity adding device 23, and the multi-pollutant detergent metering and controlling device 25, and a multi-pollutant detergent delivery pump 24 is disposed on a pipeline connecting the multi-pollutant detergent circulation tank 22 and the multi-pollutant detergent metering and controlling device 25; when the requirement on the emission limit value of low-sulfur product oil or sulfur dioxide for combustion in ships is not high, the seawater or fresh water extraction pump 21 pumps seawater to the multi-pollutant detergent circulation tank 22, and the multi-pollutant detergent delivery pump 24 delivers seawater to the multi-pollutant enhanced removal device 3 for washing and removing sulfur dioxide and fine particles such as heavy metal ions, PAH and carbon black; further, when the emission limit of the high-sulfur oil for ship combustion or sulfur dioxide is strictly required, the multi-pollutant detergent activity adding device 23 adds alkali liquor (such as magnesium hydroxide slurry) to the multi-pollutant detergent circulation tank to realize deep removal of fine particles such as sulfur dioxide, heavy metal ions, PAH and carbon black; the multi-pollutant detergent metering and controlling device 25 can regulate and record the consumption of the multi-pollutant detergent in real time.
The multi-pollutant enhanced removal device 3 comprises a multi-pollutant absorption tower 31 and a detergent variable-frequency circulating pump 32, a dense-phase enhanced mass transfer absorption area 34, a multi-pollutant detergent spray device 33 and a demister 35 are arranged in the multi-pollutant absorption tower 31 from bottom to top, and the multi-pollutant detergent spray deviceThe device 33 is communicated with the lower part of the multi-pollutant absorption tower 31 through a detergent variable-frequency circulating pump 32, and the multi-pollutant detergent metering and controlling device 25 is communicated with the lower part of the multi-pollutant absorption tower 31; the removal of fine particles such as sulfur dioxide, heavy metal ions, PAH, carbon black and the like is enhanced by coupling mass transfer and reaction processes of migration/removal of different pollutants in different scale spaces through gas-gas/gas-solid mixing, particle-liquid drop mutual collision, gas-liquid/gas-liquid-solid mass transfer and in-phase complex chemical reaction in a reaction space of the multi-pollutant absorption tower 31; the dense-phase enhanced mass transfer absorption zone 34 has the advantages of strong mixing, large specific surface area and the like by constructing the mass transfer enhanced dense-phase zone in the multi-pollutant absorption tower 31, and obviously increases SO2The desulfurization efficiency of the concentration flue gas; the multi-pollutant detergent spraying device 33 is connected with the detergent variable-frequency circulating pump 32, and the detergent variable-frequency circulating pump 32 is connected with the multi-pollutant detergent circulating tank 22; the multi-pollutant detergent spraying device can control parameters such as liquid-gas ratio, temperature, pH value and the like of detergent solution in the multi-pollutant absorption tower in real time to strengthen SO2Absorbing and trapping heavy metal ions, PAH, carbon black and other fine particles.
The integrated purification device 4 for the pollutant washing residual liquid comprises a washing residual liquid buffer tank 42, a detergent residual liquid storage tank 44, an aeration tank 47, a centrifugal separator 49, a high-voltage pulse corona reactor 412 and a water quality adjusting tank 413 which are sequentially communicated, wherein the water quality adjusting tank 413 is communicated with the washing residual liquid buffer tank 42; the bottom of the absorption tower 31 is communicated with a washing raffinate buffer tank 42 through a washing raffinate discharge pump 41, the washing raffinate buffer tank 42 is communicated with a washing raffinate storage tank 44 through a first washing raffinate delivery pump 43, the washing raffinate storage tank 44 is provided with a flocculation chelating agent adding port 45, the raffinate storage tank 44 is communicated with an aeration tank 47 through a second washing raffinate delivery pump 46, the aeration tank 47 is connected with an aeration device 48, the centrifugal separator 49 is connected with a filter press 410, and the filter press 410 is connected with a filter residue barrel 411;
adding a chelating agent into the washing residual liquid buffer tank 42 to flocculate heavy metal ions captured by the multi-pollutant enhanced removal device, then introducing the heavy metal ions into the aeration tank 47 for aeration, introducing the washing residual liquid into the centrifugal separator 49 for separation of particles and flocculation precipitation after sufficient oxidation, introducing the particles such as carbon black in the washing liquid into the centrifugal separator to separate particles with the particle size of 30-40 mu m, and then adding an aggregating agent and a flocculating agent into the residual liquid to aggregate and precipitate unseparated fine particles (the separated residue is stored in a special storage tank to be discharged to the bank); solid impurities pass through enter behind the pressure filter 410 filter sediment bucket 411, the washing liquid after the filtration subsequently gets into high voltage pulse corona reactor 412 degradation PAHs, the process the washing liquid after quality of water equalizing basin 413 is adjusted detects and discharges after reaching standard.
The sensing part collects ship information such as ship sailing position, ship speed, ship body swing and the like through sensors arranged around a ship, the sensor arranged on the side of the diesel engine 1 collects data such as operation load, exhaust emission of an outlet of the diesel engine, exhaust pollutant concentration, exhaust temperature, pressure and the like, the sensors arranged on a ship exhaust gas multi-pollutant removal and purification system and the like collect seawater parameters such as seawater temperature, pH value, alkali value and the like, the key operation and design parameters of a multi-pollutant enhanced removal device such as multi-pollutant detergent consumption, pH value, temperature, detergent spraying amount and the like, the pulse frequency, the pulse voltage and the aeration O of a high-voltage pulse power supply, and the like2The volume flow, the pH value of the aeration tank, the aeration treatment time and other key operation parameters of the integrated purification device for the washing residual liquid of the pollutants.
The waste gas generated by the side combustion of the diesel engine 1 is boosted by a booster fan and sent to a multi-pollutant reinforced removal device 3 in the device layer, a seawater extraction pump 21 extracts seawater to a multi-pollutant detergent circulation tank 22, when the emission limit of oil products with higher sulfur content or sulfur dioxide for combustion is higher in requirement, alkaline absorbent such as magnesium hydroxide and fresh water can be added to enter a multi-pollutant detergent circulation tank 22 to form high-activity multi-pollutant detergent, the detergent is conveyed to the bottom of a multi-pollutant absorption tower 31 through a multi-pollutant detergent conveying pump 24, the multi-pollutant detergent is conveyed to a multi-pollutant detergent spraying device 33 in a boosting mode through a detergent variable-frequency circulating pump 32, the multi-pollutant detergent is atomized to capture sulfur dioxide and heavy metal ions, PAH and carbon black and other fine particles in ship waste gas, the flue gas is washed and then ascends to enter a demister 35, liquid drops carried by the waste gas are further removed, and then the flue gas is discharged to the external environment through a waste gas cylinder. Meanwhile, the descending detergent and the ascending ship exhaust gas are violently mixed after meeting in the dense phase enhanced mass transfer absorption area 34, and sulfur dioxide, heavy metal ions, PAH, carbon black and other fine particles in the ship exhaust gas are further enhanced and captured.
The washing residual liquid formed after the ship exhaust gas is washed by the multi-pollutant washing agent is conveyed to a washing residual liquid buffer tank 42 through a washing residual liquid discharge pump 41, and then conveyed to a washing agent residual liquid storage tank 44 through a first washing residual liquid conveying pump 43, and adding a flocculating and sequestering agent into the detergent raffinate storage tank 44 to flocculate heavy metal ions trapped by the multi-pollutant enhanced removal device, then entering an aeration device 48 in an aeration tank 47 through a second wash raffinate delivery pump 46 for aeration, fully oxidizing the wash raffinate, then entering a centrifugal separator 49 for separating particles and flocculating and precipitating, passing solid impurities through the filter press 410 and then entering a filter residue barrel 411, passing the filtered wash liquid and then entering the high-voltage pulse corona reactor 412 for degrading PAHs, passing the wash liquid after the water quality is adjusted by the adjusting tank 413 for detecting the discharge after reaching the standard, and returning to the wash raffinate buffer tank 42 for retreatment if the discharge does not reach the standard until the discharge after reaching the standard.
In the embodiment, seawater is used as a detergent, the temperature of the seawater is 17-20 ℃, the pH value is 8.3, and the total alkalinity is 2.5 mmol/L.
SO is enhanced by adding a dense phase enhanced mass transfer absorption zone 34 and increasing pH2Absorption and removal of fine particles such as heavy metal ions, PAH, carbon black and the like.
The multi-pollutant detergent spraying device 33 can control parameters such as liquid-gas ratio, temperature, pH value and the like of the detergent solution in the multi-pollutant absorption tower in real time to strengthen SO2Absorbing and trapping heavy metal ions, PAH, carbon black and other fine particles.
The detergent solution has a design liquid-to-gas ratio of 12L/Nm3And the temperature of the washing liquid is 40 ℃. The nozzles at the bottommost layer of the multi-pollutant detergent spraying device are provided with one-way solid cone nozzles, and the rest are preferably provided with two-way solid cone nozzles.
The above-mentionedThe pulse frequency of the high-voltage pulse power supply is 180Hz, the pulse voltage is preferably 42kV, and the aeration is O2The volume flow of the treatment solution is 6L/min, the pH value is 5.5-6.0, and the treatment time is 120 min.
The optimization part collects key operation and design data of the ship and the ship waste gas multi-pollutant removal and purification system through the sensing part to construct a multi-dimensional database, and a prediction model of the multi-pollutant generation concentration, the outlet temperature and the like of the diesel engine side is established aiming at the problem that the measurement of the concentration of the pollutants at the inlet of the multi-pollutant enhanced removal device 3 is delayed or inaccurate due to the complex and changeable navigation working conditions. Further based on the process characteristics of generating and removing the multiple pollutants in the ship exhaust gas, determining key factors influencing the generation and removal of the pollutants, establishing a multiple pollutant concentration generation-removal prediction model, and realizing the accurate prediction of the multiple section pollutant concentration.
The establishment of the multi-pollutant concentration generation-removal prediction model specifically comprises the following steps:
s1: collecting key operation and design parameters of the ship and ship exhaust gas multi-pollutant removal and purification system collected by the sensing layer, and establishing a multi-dimensional database covering key parameters of ship exhaust gas pollutant emission reduction system design, operation, energy consumption, material consumption and the like;
s2: establishing a diesel side SO2 generated concentration prediction model through key parameters of a diesel side, such as load, combustion air supply quantity, temperature, oxygen quantity and the like;
s3: SO removal device based on multiple pollutants2Mechanism, establishes that seawater is used as a washing agent to remove SO2The mechanism model of the method is modified by historical data, and corresponding relations between the concentration, the temperature, the spraying amount of a detergent, the slurry density, the pH value, the ship inclination angle, the sailing area and the like of seawater and a magnesium hydroxide method desulfurization inlet SO2 and the concentration of a multi-pollutant removal device outlet SO2 are respectively obtained;
s4: meanwhile, historical operation data and test data are further utilized, and a data modeling method is utilized to obtain the corresponding relation between the inlet particle concentration of the multi-pollutant enhanced removal device, the inlet exhaust gas temperature, the detergent spraying amount, the slurry density, the pH value, the ship inclination angle and the like and the outlet particle concentration of the multi-pollutant removal device and Polycyclic Aromatic Hydrocarbons (PAHs);
s5: based on the corresponding relations, the prediction deviation of the correction model is utilized to train data models such as a deep neural network and a random forest on the basis, the prediction precision and the generalization capability of the models are further improved, a multi-pollutant concentration generation-removal prediction model is established, and the accurate prediction of the multi-section pollutant concentration is realized.
Side SO of the diesel engine2The concentration prediction model was generated as follows:
Y＝f(X,V0,T,S,β,ɑ)
wherein Y is the side SO of diesel engine2Formation concentration, X is load, V0The method is characterized in that the method is used for solving the problem that the air quantity is theoretical air quantity of combustion, T is boiler side temperature, S is fuel oil sulfur content, alpha is an excess air coefficient, and beta is incomplete combustion loss of a diesel engine machine.
The multi-pollutant reinforced removing device outlet SO2The concentration prediction model is as follows:
W＝f(Y,Q,T1,ρ,I,Θ)
in the formula, W is the outlet SO of the multi-pollutant reinforced removal device2Concentration, Y is side SO of diesel engine2The concentration of the product, Q detergent spray amount, rho is the slurry density, I is the pH value, T1And theta is the ship inclination angle for the inlet side temperature of the multi-pollutant reinforced removal device.
The pollutant concentration prediction model established by the optimization part realizes the advanced prediction of pollutant emission data under the current working condition, the control part is utilized to realize the switching of the multi-pollutant detergent in advance, namely seawater or magnesium hydroxide is adopted as an absorption detergent, the key operation parameters of the multi-pollutant enhanced removal device are adjusted to be accurately adjusted and optimally regulated, the automatic start and stop of key equipment are realized, and further, the energy conservation and consumption reduction are realized, the emission stability is improved, and the consumption of environmental pollutants and resources is reduced.
The ship exhaust gas adopts fuel oil with 3.1 percent of sulfur content as fuel, and SO in the ship exhaust gas discharged after being treated by the embodiment at 71.4 percent of load2/CO2The ratio of the fuel oil to the water is stabilized at about 1.08, and the problem of poor combustion of the ship in a complex navigation environment is solved at low costSO caused by oil products2The problem of standard exceeding of emission is solved, and the adaptability of the ship to complex working conditions in the running process is improved; meanwhile, the intelligent switching between open-loop and closed-loop desulfurization modes is realized by using an intelligent regulation and control method, SO that SO (sulfur oxide) is reduced2The discharge fluctuation saves the material consumption and the power consumption of alkali liquor, fresh water and the like, and further reduces the operating intensity of crew, and the like; meanwhile, by combining the standby points of limited installation space, limited reaction time and small treated water amount in the ship environment, a green, energy-saving, efficient and compact ship desulfurization and washing water post-treatment system is developed, the temperature of the treated wastewater is about 19.2 ℃, the Polycyclic Aromatic Hydrocarbons (PAHs) are lower than 2.9 micrograms/liter, and the efficient treatment of the ship wastewater is realized.
Example 2
On the basis of the embodiment 1, in the embodiment, because the navigation area span is large, the sulfur content of the fuel oil is lower than 1.0 percent, the corresponding sulfur emission requirement is high, the magnesium hydroxide alkaline absorbent is adopted as an enhancer for enhancing the removal of pollutants such as sulfur dioxide, the pH value of the detergent solution is controlled to be 6.5, and the liquid-gas ratio is about 15L/Nm3And the temperature of the washing circulating liquid is 40 ℃. The ship is influenced by weather in the sailing environment, the inclination angle is 0-10 degrees, the operation and test data of the purification system are collected for reducing the influence on the operation effect of the multi-pollutant removal device in the bumpy environment, the relation between the desulfurization efficiency and the flue gas volume of the purification system under different inclination angles is simulated by using an optimization computing platform, the desulfurization efficiency under different operation environments and operation loads is predicted in advance by using simulation results, the sulfur dioxide removal efficiency is up to more than 94 percent, and SO is reduced2The discharge is fluctuant, and the material consumption and the power consumption of alkali liquor, fresh water and the like are saved; meanwhile, the multi-pollutant washing residual liquid integrated purification device can reduce the content of Polycyclic Aromatic Hydrocarbons (PAHs) in the residual liquid by more than 80% after the washing residual liquid is treated, and realize the high-efficiency treatment of the ship wastewater.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The utility model provides a green, high-efficient boats and ships waste gas multi-contaminant desorption clean system which characterized in that: the system comprises a device part, a sensing part, a control part and an optimization part,
the device part comprises a marine diesel engine, a multi-pollutant detergent preparation device, a multi-pollutant reinforced removal device, a multi-pollutant washing residual liquid integrated purification device and an exhaust gas exhaust funnel, and sulfur dioxide is absorbed and removed and heavy metal ions, PAH, carbon black and other fine particles are washed and removed through physical and chemical reactions;
the sensing part comprises an instrument for acquiring various data and a processor for analyzing the data, and information acquisition, preprocessing, integration, storage and distribution are carried out through an instrument on-line detection device and other sensing and communication equipment;
the control part comprises a valve, a pump and other linkage control devices, and key operation quantity adjustment is carried out through real-time operation working conditions and optimized parameter setting, so that the system is ensured to be stable and reach the standard and optimized and adjusted;
the optimization part comprises a calculation platform constructed by a pollutant generation concentration and outlet pollutant concentration prediction model, realizes intelligent switching of desulfurization operation modes under frequent change of navigation environment and frequent fluctuation of load, and
and (3) accurately adjusting and optimally regulating and controlling key parameters of system operation.
2. The green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 1, is characterized in that: the multi-pollutant detergent preparation device comprises a multi-pollutant detergent circulation tank, a seawater or fresh water extraction pump, a multi-pollutant detergent activity adding device and a multi-pollutant detergent metering and regulating device, wherein an alkali liquor is arranged in the multi-pollutant detergent activity adding device, the multi-pollutant detergent circulation tank is respectively connected with the seawater or fresh water extraction pump, the multi-pollutant detergent activity adding device and the multi-pollutant detergent metering and regulating device, and a multi-pollutant detergent delivery pump is arranged on a pipeline connecting the multi-pollutant detergent circulation tank and the multi-pollutant detergent metering and regulating device;
the multi-pollutant washing agent metering and regulating device is communicated with the lower part of the multi-pollutant absorption tower;
the integrated purification device for the pollutant washing residual liquid comprises a washing residual liquid buffer tank, a detergent residual liquid storage tank, an aeration tank, a centrifugal separator, a high-voltage pulse corona reactor and a water quality adjusting tank which are sequentially communicated, wherein the water quality adjusting tank is communicated with the washing residual liquid buffer tank; the bottom of the absorption tower is communicated with a washing residual liquid buffer tank through a washing residual liquid discharge pump, the washing residual liquid buffer tank is communicated with a detergent residual liquid storage tank through a first washing residual liquid delivery pump, a flocculating and sequestering agent adding port is arranged on the detergent residual liquid storage tank, the residual liquid storage tank is communicated with an aeration tank through a second washing residual liquid delivery pump, the aeration tank is connected with aeration equipment, a centrifugal separator is connected with a filter press, and the filter press is connected with a filter residue barrel.
3. The green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 2, is characterized in that: in the multi-pollutant detergent preparation device, seawater is used as a detergent, the pH value of a detergent solution is controlled to be 7.5-8.3, and the total alkalinity is 2.0-3.0 mmol/L; the alkali liquor is magnesium hydroxide slurry, the magnesium hydroxide slurry is used as a detergent, the pH value of a detergent solution is controlled to be 5.0-6.5, and the molar ratio of magnesium to sulfur is not more than 1.05;
much sewageIn the dye reinforced removing device, seawater is used as a washing agent, and SO is reinforced by additionally arranging a dense phase region and increasing pH2Absorbing and removing heavy metal ions, PAH carbon black and other fine particles; magnesium hydroxide slurry is used as a washing agent, and SO is strengthened by adjusting liquid-gas ratio and adding a dense-phase region2Absorption and removal of heavy metal ions, PAH, carbon black and other fine particles;
seawater is used as a detergent, and the liquid-gas ratio of the detergent solution is not less than 10L/Nm3Controlling the temperature to be 15-30 ℃; the magnesium hydroxide slurry is used as a detergent, and the liquid-gas ratio of the detergent solution is more than 5L/Nm3And controlling the temperature to be 40-52 ℃.
4. The green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 2, is characterized in that: the nozzles at the bottommost layer of the multi-pollutant detergent spraying device are provided with one-way solid cone nozzles, and the rest are provided with two-way solid cone nozzles.
5. The green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 2, is characterized in that: the pulse frequency of the high-voltage pulse power supply is 180Hz, the pulse voltage is 42kV, and the aeration is carried out2The volume flow of the treatment solution is 6L/min, the pH value is controlled to be 5.5-6.0, and the treatment time is 120 min.
6. The intelligent regulation and control method of the green and high-efficiency ship exhaust gas multi-pollutant removal and purification system of claim 1 is characterized by comprising the following steps:
(1) the sensing part collects key operation and design parameters of the ship and the ship waste gas multi-pollutant removal and purification system through arranged instruments and sensors;
(2) the optimization part collects key operation and design parameters of the ship and ship waste gas multi-pollutant removal and purification system through the sensing part to construct a multi-dimensional database and establish a multi-pollutant concentration generation-removal prediction model;
(3) based on the model, the pollutant emission data under the current working condition is predicted in advance, the control part is utilized to realize the switching of the multi-pollutant detergent in advance, and the key operation parameters of the multi-pollutant enhanced removal device are adjusted to be accurately adjusted and optimally regulated.
7. The intelligent regulation and control method of the green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 6, characterized in that: the key operation and design parameters in the step (1) comprise ship information including ship sailing position, speed and ship body swing, diesel engine operation load, diesel engine outlet exhaust emission, exhaust pollutant concentration, exhaust gas temperature, exhaust gas pressure, seawater temperature, seawater pH value, seawater alkali value, multi-pollutant detergent consumption, pH, temperature, detergent spraying amount, high-voltage pulse power supply pulse frequency, pulse voltage, aeration O2Volume flow, pH value of aeration tank and aeration treatment time.
8. The intelligent regulation and control method for the green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 6 or 7, characterized in that the establishment of the multi-pollutant concentration generation-removal prediction model specifically comprises the following steps:
s1: collecting key operation and design parameters of the ship and the ship waste gas multi-pollutant removal and purification system collected by the sensing part, and establishing a multi-dimensional database covering key parameters of ship waste gas pollutant emission reduction system design, operation, energy consumption and material consumption;
s2: establishing a diesel engine side SO through the diesel engine side including load, combustion air supply quantity, temperature and oxygen quantity key parameters2Generating a concentration prediction model;
s3: SO removal device based on multiple pollutants2Mechanism, respectively establishes that seawater and alkali liquid absorbent are used as detergents to remove SO2By utilizing the historical data correction model, the seawater and alkali liquor absorption liquid method desulfurization inlet SO are respectively obtained2Concentration, temperature, detergent spraying amount, slurry density, pH value, ship inclination angle, navigation area and multi-pollutant removal device outlet SO2The corresponding relation of concentration;
s4: meanwhile, further utilizing historical operation data and test data and utilizing a data modeling method to respectively obtain corresponding relations between the concentration of particles at the inlet of the seawater and alkali liquor absorbent desulfurization process, the temperature of inlet waste gas, the spraying amount of a washing agent, the density of slurry, the pH value, the inclination angle of a ship, the concentration of particles at the outlet of the multi-pollutant removal device and polycyclic aromatic hydrocarbon;
s5: based on the corresponding relation, the deep neural network and the random forest data model are trained by utilizing the prediction deviation of the correction model on the basis, the prediction precision and the generalization capability of the model are further improved, a multi-pollutant concentration generation-removal prediction model is established, and the accurate prediction of the multi-section pollutant concentration is realized.
9. The intelligent regulation and control method for the green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 8, wherein the SO at the side of the diesel engine is used as the SO2The concentration prediction model was generated as follows:
Y＝f(X,V0,T,S,β,ɑ)
wherein Y is the side SO of diesel engine2Formation concentration, X is load, V0The method is characterized in that the method is used for solving the problem that the air quantity is theoretical air quantity of combustion, T is boiler side temperature, S is fuel oil sulfur content, alpha is an excess air coefficient, and beta is incomplete combustion loss of a diesel engine machine.
10. The intelligent regulation and control method for the green and high-efficiency ship exhaust gas multi-pollutant removal and purification system according to claim 8, wherein the SO at the outlet of the multi-pollutant removal strengthening device2The concentration prediction model is as follows:
W＝f(Y,Q,T1,ρ,I,Θ)
in the formula, W is the outlet SO of the multi-pollutant reinforced removal device2Concentration, Y is side SO of diesel engine2The concentration of the product, Q detergent spray amount, rho is the slurry density, I is the pH value, T1And theta is the ship inclination angle for the inlet side temperature of the multi-pollutant reinforced removal device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113996286A (en) * | 2021-10-20 | 2022-02-01 | 浙江程润云环境科技有限公司 | High-mechanical-strength thin-wall sulfur-resistant ship denitration catalyst and preparation method thereof |
| CN114159968A (en) * | 2021-12-10 | 2022-03-11 | 山西大学 | Prediction method for cooperative control of heavy metal pollutants in power plant flue gas |
| CN114294078A (en) * | 2022-01-04 | 2022-04-08 | 江南造船(集团)有限责任公司 | Marine diesel engine exhaust gas cleaning system |
| CN115414770A (en) * | 2022-09-15 | 2022-12-02 | 杭州楚环科技股份有限公司 | Garbage waste gas treatment method |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113996286A (en) * | 2021-10-20 | 2022-02-01 | 浙江程润云环境科技有限公司 | High-mechanical-strength thin-wall sulfur-resistant ship denitration catalyst and preparation method thereof |
| CN114159968A (en) * | 2021-12-10 | 2022-03-11 | 山西大学 | Prediction method for cooperative control of heavy metal pollutants in power plant flue gas |
| CN114159968B (en) * | 2021-12-10 | 2023-09-26 | 山西大学 | Prediction method for cooperative control of heavy metal multi-pollutants in power plant flue gas |
| CN114294078A (en) * | 2022-01-04 | 2022-04-08 | 江南造船(集团)有限责任公司 | Marine diesel engine exhaust gas cleaning system |
| CN115414770A (en) * | 2022-09-15 | 2022-12-02 | 杭州楚环科技股份有限公司 | Garbage waste gas treatment method |
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