CN117547970B - Photo-thermal catalysis ship exhaust gas treatment method - Google Patents
Photo-thermal catalysis ship exhaust gas treatment method Download PDFInfo
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Abstract
The invention belongs to the field of waste gas purification treatment, and provides a method for treating ship waste gas by photo-thermal catalysis, which is used for obtaining dust-free waste gas by filtering organic waste gas to be purified to remove particulate matters and viscous components; the organic matters in the dust-free waste gas are adsorbed by the adsorbing material to obtain organic waste gas; carrying out catalytic degradation reaction on the organic waste gas in a purification system to obtain purified gas; and in the catalytic degradation reaction, the catalytic module in the purification system is dynamically controlled in real time. The position of the deactivation trend in the infrared thermal image can be accurately identified, and the temperature and/or the light intensity can be accurately controlled in real time so that the deactivation intensity of the dark catalytic material reaches a safe level; under the severe environment of high-heat continuous ship exhaust gas, the effect duration of improving the activity of the catalyst is prolonged, and the service life of the catalyst for photo-thermal catalysis of ship exhaust gas treatment is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a method for treating ship waste gas by photo-thermal catalysis.
Background
The engine of modern ships mainly takes diesel engine as main fuel and marine heavy oil as fuel, and the ships can discharge VOCs (volatile organic compounds) to the atmosphere through the volatilization and combustion of the engine fuel in the loading, unloading and cruising processes, and mainly comprise alkanes (such as propane) and aromatic hydrocarbon substances (such as benzene, toluene and xylene).
Aiming at the problem of processing VOCs in ship exhaust gas, the method for processing the VOCs at present mainly adopts the following steps: the condensation method, adsorption method, combustion method, etc., and the specific problems of these prior arts are: (1) condensation method: the method is suitable for treating the waste gas with high concentration, low temperature and small air quantity, so the method is not generally adopted for pollution control of VOCs in the high-heat ship waste gas, and the ship waste gas has the characteristics of large air quantity, long duration and high temperature, and the existing condenser cannot load the high-heat ship waste gas with large and durable air quantity. (2) adsorption method: the adsorption method is suitable for treating waste gas with low concentration and no need of recovering pollutant. However, the activated carbon is not suitable for ship exhaust gas, and the adsorber cannot purify organic exhaust gas for a long time due to long-term drifting operation of the ship in a river or at sea, so that the adsorbent which needs to be replaced periodically is difficult to replace, and the operation cost is high. (3) combustion method: although the method has low energy consumption, high purification rate, no secondary pollution, simple process and convenient operation, the method is not suitable for treating the ship exhaust gas due to the problems of large air quantity and long duration of the ship exhaust gas.
At present, a ship waste gas is more suitable to be an adsorption concentration-catalytic combustion method, in the treatment process of VOCs in the ship waste gas, a catalytic system is usually in a thermal catalysis mode of providing energy by an external heat source, for example, chinese patent publication No. CN109011868B discloses a catalytic system, application thereof and a purification method and a purification system of organic waste gas, the purification method of organic waste gas comprises the steps of carrying out photo-thermal catalytic degradation reaction or photo-thermal synergistic catalytic degradation reaction on the organic waste gas to be purified in the presence of the catalytic system, the catalytic system consists of a dark catalytic material and a light source, and the light source irradiates on the dark catalytic material to generate enough heat to initiate the thermal catalytic reaction or photo-thermal synergistic catalytic reaction, although the catalytic system adopts the light source to irradiate on the surface of the dark catalytic material to spontaneously generate enough heat to initiate the thermal catalytic reaction or photo-thermal synergistic catalytic reaction, so that the purification efficiency of the organic waste gas can be improved, and high-efficiency energy conservation can be realized. However, the alumina-supported platinum catalyst (Pt/Al 2 O 3 ) Or alternativelyManganese dioxide loaded platinum catalyst (Pt/MnO) 2 ) Is irradiated to the fixed 500-1000 mW/cm of the catalyst bed layer through full spectrum solar light 2 The high intensity of the light intensity of (a) is used for accelerating the heat, and the environment temperature is low, under the conditions of high temperature (the ship exhaust gas inlet temperature and the exhaust gas outlet temperature are generally about 170 ℃ to 500 ℃), high oxidation environment, large air quantity, long duration and severe steam, the loaded platinum catalyst can be quickly deactivated, the loss performance or the performance is reduced, the main deactivation path is through sintering, in the process, the initial small Nano Particles (NPs) grow into larger nano particles, and the active surface area is reduced (see reference documents: aitbekova A, zhou C, stone M L, et al, templated encapsulation of platinum-based catalysts promotes high-temperature stability to 1,100 degrees C[J)]Nature materials, 2022). Although this study in the reference has proposed a new material encapsulated platinum/alumina catalyst (pt@al 2 O 3 ) To replace the prior alumina-supported platinum catalyst (Pt/Al 2 O 3 ) Or manganese dioxide supported platinum catalyst (Pt/MnO) 2 ) The material, however, the packaging technology of the new catalyst material is complex, the production cost is high, and the catalytic activity of the packaged catalyst is slightly inferior to that of the existing alumina-supported platinum catalyst (Pt/Al 2 O 3 ) Or manganese dioxide supported platinum catalyst (Pt/MnO) 2 ) A material.
Disclosure of Invention
The invention aims to provide a method for treating ship exhaust gas by photo-thermal catalysis, which solves one or more technical problems in the prior art and at least provides a beneficial choice or creation condition.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method of photo-thermally catalyzing exhaust gas treatment of a ship, the method comprising the steps of:
filtering the organic waste gas to be purified to remove particulate matters and viscous components to obtain dust-free waste gas;
adsorbing organic matters in the dust-free waste gas by using an adsorption material to obtain organic waste gas;
carrying out catalytic degradation reaction on the organic waste gas in a purification system to obtain purified gas;
wherein, during the catalytic degradation reaction, the catalytic module in the purification system is dynamically controlled in real time;
the method for dynamically controlling the catalytic module in the purification system in real time comprises the following steps:
collecting an infrared thermal imaging image of a dark catalytic material in the catalytic module;
identifying performance degradation positions of the dark catalytic material through an infrared thermal imaging graph;
calculating the inactivation strength of the dark catalytic material according to the performance degradation position;
the temperature and/or light intensity is controlled in real time to bring the deactivated intensity of the dark catalytic material to a safe level.
Further, the method for identifying the performance degradation position of the dark catalytic material through the infrared thermal imaging graph comprises the following steps:
the method comprises the steps of regularly acquiring an infrared thermal imaging image of a dark catalytic material, improving the irradiation intensity of a light source for a preset time on the dark catalytic material before each acquisition of the infrared thermal imaging image, and reducing the irradiation intensity of the light source when each acquisition of the image is completed; (the purpose of improving the irradiation intensity is to temporarily enable the dark catalytic material to generate heat contrast between each region with reduced activity and each region with larger activity in infrared imaging, and the temperature difference caused by spontaneous heat generation on the surface of the dark catalytic material due to irradiation of a light source on each position of the dark catalytic material is presented on an infrared thermal imaging image, so that the acquired images can show the difference of activity change of each position of the dark catalytic material), the acquired thermal infrared images are converted into gray images, and edges in the gray images are obtained by edge detection; dividing the gray image into a plurality of sections by each edge; selecting an interval of which the average gray value of each pixel in the interval is smaller than the average gray value of each pixel in the position of the interval corresponding to the infrared thermal imaging image acquired in the previous time, and marking the interval as an activity weakening position; the active weakness position with the largest average gray value of each pixel in each active weakness position is noted as a performance degradation position (the performance degradation position is the position in the dark catalytic material which is degrading or just degrading performance), and then each infrared thermal imaging map corresponds to one performance degradation position.
The performance reduction position is the region with the most obvious performance reduction in the dark catalytic material, can fully show the gradual change temperature difference when the dark catalytic material is about to be deactivated, and is likely to generate a deactivation trend, so that the temperature change trend of the dark catalytic material in a limiting illumination state is accurately captured, the change range of the catalytic material along with the increase of the illumination temperature is smaller if the dark catalytic material is about to be deactivated, and the change range along with the increase of the illumination temperature is larger if the activity is better.
Further, the method for calculating the deactivation strength of the dark catalytic material according to the performance degradation position comprises the following steps:
recording the acquisition times corresponding to the infrared thermal imaging graph as [1, N ] times, wherein N is the last acquisition time; recording the performance degradation position corresponding to the infrared thermal imaging image acquired for the nth time as LC (N); taking the performance degradation position with the minimum average gray value of each pixel in each performance degradation position as an anchor position; taking the performance degradation position with the maximum average gray value of each pixel in each performance degradation position as a target position; (since the deactivation of the dark catalytic material is not completely deactivated in a whole moment, but gradually diffuses from a small area to a large area, there is a longer deactivation process, and since a large temperature difference is generated between the deactivated small area and other normal areas nearby, so that a large difference is generated between the heat transfer of the deactivated area and the non-deactivated area, and the deactivation rate of other areas nearby is changed, so that the anchor position and the target position are defined for accurately and intelligently sensing the slight change trend, the diffusion transfer of the deactivation of the dark catalytic material tends to be transferred from the anchor position to the target position, and because the change is irregular and not linearly changed, there is possibility that the Nth-1 infrared thermal imaging image is diffused, but the Nth infrared thermal imaging image is compared with the Nth-1 infrared thermal imaging image, and the diffusion of the performance-reducing position does not occur, so that the transfer trend is not directly sensed by infrared imaging);
recording corresponding projection positions of the anchor position and the target position on a gray level image of an Nth acquired infrared thermal imaging image as an LC1 region and an LC2 region, taking a point with the largest difference value of gray level values in the anchor position and the LC1 region as an anchor point ancP1 and a point with the smallest difference value as an anchor point ancP2, and taking a point with the largest difference value of gray level values in the target position and the LC2 region as a target point tagP1 and a point with the smallest difference value as an anchor point tagP2; taking a quadrilateral area formed by four points of angP 1, tagP1, angP 2 and tagP2 as a performance-reducing transmission area; (the reduced performance transfer areas selected by the 4 dot frames are the areas in which reduced performance transfer may occur in each infrared thermal imaging image, some infrared thermal imaging images may occur in the areas, and some infrared thermal imaging images may not occur in the areas, and it is noted that there are many times when there is no time-series correlation between the infrared thermal imaging images in which the reduced performance positions occur, the occurrence timing and the positions are more random, but all are within the range, and the reduced performance positions in other positions outside the reduced performance transfer areas are not necessarily truly reduced performance, and the reduced performance positions in other positions may not be truly positions that cause reduced performance nor have transmissibility because they are not reduced performance trends transferred by the anchor positions);
taking the corresponding projection positions of the reduced performance transfer areas on all the infrared thermal imaging images as reduced performance transfer projection areas of each infrared thermal imaging image; forming a sequence of all performance-degrading positions in the performance-degrading transmission projection area according to the acquisition time sequence of the corresponding infrared thermal imaging image as a position queue, and sequentially calculating the inactivation intensity of each performance-degrading position;
the calculation method for calculating the inactivation intensity LoseStr (i) of the ith performance degradation position comprises the following steps: taking the average gray value of each point in the performance-reducing position as the performance gray, and recording the number of performance gray increase between every two performance gray in each performance gray from the 1 st performance-reducing position to the i th performance-reducing position in the position queue as UPN (i) and the number of performance gray decrease between every two performance gray as DON (i); loseStr (i) =upn (i)/(UPN (i) +don (i)) ×100; (the multiplication of 100 at the rear is to limit the value of the inactivation intensity between 0 and 100 to facilitate setting of the threshold value, the inactivation intensity is large when the value is large, whereas the inactivation intensity is small).
The average deactivation intensity of the deactivation intensity of all performance-degrading sites is taken as the deactivation intensity of the dark catalytic material.
Where i is the sequence number of the degraded performance location in the location queue.
According to the principle that the heat generated by the infrared thermal imaging graph is changed when the dark catalytic material is excited by the light source to trigger the thermal catalytic reaction in the deactivation process, the relative deactivation intensity change of the dark catalytic material in the deactivation process can be accurately calculated, so that whether certain positions of the dark catalytic material are deactivated or are about to be deactivated is further judged. And if the deactivation intensity is higher than a preset threshold value, judging that the dark catalytic material is in the tendency of being deactivated. However, the threshold value of the method is fixed, and the deactivation strength is quite probably not up to the set threshold value, but the deactivation strength of the same performance-reducing position, which is continuously not up to the threshold value, is accumulated, so that the dark catalytic material of the performance-reducing position can be suddenly deactivated instantaneously, and in order to prevent the phenomenon, the method for calculating the deactivation strength is improved:
let i be the serial number of the performance-degrading position in the position queue, record the maximum temperature value of each point in the ith performance-degrading position as SlowMax (i) and the minimum temperature value as SlowMin (i); within the range of i, marking an i-th reduced performance location and an i-1-th reduced performance location to produce reduced performance transfer between the i-th reduced performance location and the i-1-th reduced performance location if the i-th reduced performance location meets the conditions SlowMax (i-1) +overly (i-1, i) and SlowMin (i). Gtoreq.SlowMin (i-1) -overly (i-1, i);
wherein, the overlap (i) is the degradation transfer superposition value of the ith degradation position, and the calculation method is as follows:
；
PN is the number of performance-degrading positions in the position queue, j is a variable, and SMAx (i, j) is the difference between the maximum temperature value of each point in the ith performance-degrading position and the maximum temperature value of each point in the jth performance-degrading position; SMin (i, j) is the difference between the minimum temperature value for each point in the ith reduced performance location and the minimum temperature value for each point in the jth reduced performance location; smaxG (i, i-1) is the difference between the maximum temperature value for each point in the ith reduced performance location and the maximum temperature value for each point in the ith-1 reduced performance location; sminG (i, i-1) is the difference between the minimum temperature value for each point in the ith reduced performance location and the minimum temperature value for each point in the ith-1 reduced performance location;
the degradation transfer overlapping value is the average value obtained by overlapping the degradation positions in the historical position queue and the variation degrees of all the generated temperature differences of the current degradation positions, so that the continuous inactivation strength which does not reach the threshold value of the same degradation position can be accurately reflected, the variation strength of the degradation position which can suddenly cause the instant inactivation of the dark catalytic material of the degradation position is accumulated, and whether the current degradation position which does not reach the threshold value can generate degradation transfer or not can be accurately captured.
The calculation method of the inactivation intensity LoseStr (i) for calculating the ith performance degradation position is as follows: taking the average gray value of each point in the performance-reducing positions as the performance gray, marking all adjacent two performance-reducing positions which generate performance-reducing transmission in all performance-reducing positions from 1 to i sequence numbers as transmission groups, counting the number of transmission groups with increased performance gray among all transmission groups as UPNumG (i), and counting the number of transmission groups with decreased performance gray among all transmission groups as DONumG (i);
the inactivation intensity LoseStr (i) =upnumgo (i)/(upnumgo (i) +donumo (i)) ×100; (the multiplication of 100 at the rear is to limit the value of the inactivation strength to between 0 and 100, and the inactivation strength is large when the value is large, whereas the inactivation strength is small).
The average deactivation intensity of the deactivation intensity of all performance-degrading sites is taken as the deactivation intensity of the dark catalytic material.
The method utilizes stronger temperature difference fluctuation among various historical transmission groups to amplify the inactivation strength of the ith performance degradation position, thereby accurately representing the speed and strength of performance degradation transmission in the ith performance degradation position, improving the control precision and accurately identifying the performance degradation position with weaker performance degradation transmission rate but continuous performance degradation transmission in subsequent calculation.
Further, the method for controlling the temperature and/or the light intensity in real time to ensure that the deactivation intensity of the dark catalytic material reaches a safe level is specifically as follows: when the deactivation intensity is greater than the set high threshold, the illumination intensity to the dark catalytic material is reduced and/or the temperature of the catalytic module is reduced until the deactivation intensity at the performance-degrading location of the newly acquired infrared thermal imaging map is reduced to a safe level.
Wherein the safety level is the lowest value of the inactivation intensity of the historical performance degradation sites, or the safety level is the average value of the inactivation intensity of each performance degradation site.
Alternatively, the safety level is such that the value of the deactivation strength is 20 or less. Preferably, the high threshold is a value of 80 for the deactivation intensity.
Preferably, the method for controlling the light intensity in real time comprises the following steps:
when the current light intensity Inten of the light source is Inten epsilon (0.5 xBInt, 0.8 xBInt), the current light intensity of the light source is reduced by 10%, and when the current light intensity Inten of the light source is Inten epsilon (0.8 xBInt, BInt), the current light intensity of the light source is reduced by 20%, wherein BInt is the maximum light intensity of the light source.
Preferably, the method for reducing the current light intensity of the light source is as follows: the light source reduces and adjusts the light intensity through a dimmer or an illumination controller.
Preferably, the method for controlling the temperature in real time comprises the following steps:
when the temperature Temp of the catalytic module is Temp epsilon (0.5 XBTem, 0.8 XBTem), the temperature of the catalytic module is reduced by 10%, and when the temperature Temp of the catalytic module is Temp epsilon (0.8 XBTem, BTem), the temperature of the catalytic module is reduced by 20%, wherein BTem is a set temperature threshold.
Preferably, the method of reducing the temperature of the catalytic module is by water cooling or compression refrigeration.
Further, the purification system comprises a filtering module, an adsorption module and a catalytic module which are sequentially communicated, wherein an adsorption material is arranged in the adsorption module, a thermal infrared imager, a light source and a dark catalytic material are arranged in the catalytic module, and organic waste gas is sequentially introduced into the filtering module, the adsorption module and the catalytic module to respectively carry out dust removal, gas adsorption and catalytic degradation reaction on the organic waste gas; the light source irradiates on the dark catalytic material to generate enough heat to initiate a thermocatalytic reaction or a photo-thermal synergistic catalytic reaction.
Further, the infrared thermal imaging image is obtained by scanning the dark catalytic material in the catalytic module through a thermal imager.
Further, the active substances in the dark catalytic material are a mixture of noble metal, transition metal oxide and carbon material;
the transition metal oxide is selected from at least one of manganese oxide, cobalt oxide, nickel oxide and tungsten oxide;
the carbon material is at least one selected from fullerene, carbon fiber, carbon nanotube, carbon aerogel, graphene and activated carbon;
the noble metal material is selected from at least one of gold, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum;
the weight ratio of the content of the noble metal to the total content of other active substances and carriers without catalytic activity is 1: (20-1000);
the light source is selected from at least one of ultraviolet light, visible light, infrared light and full-spectrum sunlight; the light intensity of the light source is 500-2000mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The light source is adjusted to increase or decrease the light intensity through a dimmer or an illumination controller.
The adsorption material is at least one selected from activated carbon, zeolite molecular sieve, activated alumina, silica gel and resin.
Preferably, the adsorbent material is honeycomb activated carbon.
The beneficial effects of the invention are as follows: the invention provides a method for treating ship exhaust gas by photo-thermal catalysis, which can accurately identify the position of deactivation trend in an infrared thermal image, and accurately control temperature and/or light intensity in real time so as to ensure that the deactivation intensity of a dark catalytic material reaches a safe level; under the severe environment of high-heat continuous ship exhaust gas, the effect duration of improving the activity of the catalyst is prolonged, and the service life of the noble metal catalyst for photo-thermal catalysis of ship exhaust gas treatment is greatly prolonged.
Drawings
The above and other features of the present invention will become more apparent from the detailed description of the embodiments thereof given in conjunction with the accompanying drawings, in which like reference characters designate like or similar elements, and it is apparent that the drawings in the following description are merely some examples of the present invention, and other drawings may be obtained from these drawings without inventive effort to those of ordinary skill in the art, in which:
fig. 1 is a system configuration diagram of a photo-thermal catalytic ship exhaust gas treatment.
Detailed Description
The conception, specific structure, and technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects, and effects of the present invention. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
Example 1
Filtering the organic waste gas to be purified to remove particulate matters and viscous components to obtain dust-free waste gas;
adsorbing organic matters in the dust-free waste gas by using an adsorption material to obtain organic waste gas;
carrying out catalytic degradation reaction on the organic waste gas in a purification system to obtain purified gas;
wherein, during the catalytic degradation reaction, the catalytic module in the purification system is dynamically controlled in real time;
the method for dynamically controlling the catalytic module in the purification system in real time comprises the following steps:
collecting an infrared thermal imaging image of a dark catalytic material in the catalytic module;
identifying performance degradation positions of the dark catalytic material through an infrared thermal imaging graph;
calculating the inactivation strength of the dark catalytic material according to the performance degradation position;
the light intensity is controlled in real time so that the deactivation intensity of the dark catalytic material reaches a safe level.
The purification system adopted in this embodiment includes a filtration module, an adsorption module and a catalytic module that are sequentially communicated, the filtration module is a dry filter, the adsorption module is an adsorption column filled with an adsorption material (the adsorption material is honeycomb activated carbon), a catalyst bed, a thermal infrared imager and a light source are arranged in the catalytic module, the catalyst bed includes a deep color catalytic material (the deep color catalytic material is a manganese dioxide loaded platinum catalyst (Pt/MnO) 2 ) Wherein Pt is supported on MnO 2 And Pt and MnO 2 The weight ratio of (2) is 1:100 And a light source (the light source is full spectrum sunlight) and the light intensity of the light irradiated to the catalyst bed layer is 1000mW/cm 2 One of the exhaust outlets of the catalytic module is communicated with the inlet of the adsorption module.
The method comprises the following specific steps of filtering organic waste gas to be purified to remove particulate matters and viscous components to obtain dust-free waste gas:
the organic waste gas to be purified (the organic waste gas is derived from ship waste gas, and the organic waste gas to be purified accords with GB15097-2016 (first and second stages of China) emission limit and measurement method of exhaust pollutants of ship engines, GB20891-2014 (third and fourth stages of China) emission limit and measurement method of exhaust pollutants of diesel engines for non-road mobile machinery, GB3552-2018 emission standard of ship pollutants and GB4286-84 emission standard of industrial pollutants of ships) at 4000m 3 The flow rate of/h is introduced into a dry air filter by an induced draft fan for filtering to remove particulate matters in the dry air filter so as to obtain dust-free waste gas.
The specific steps for obtaining the organic waste gas by adsorbing the organic matters in the dust-free waste gas through the adsorbing material are as follows:
adsorbing organic matters in the dust-free waste gas by using an adsorption material in an adsorption module, wherein the volume space velocity of the adsorption is 40000h -1 。
The method comprises the following specific steps of carrying out catalytic degradation reaction on organic waste gas in a purification system to obtain purified gas:
the organic waste gas passes through a catalyst bed layer in the catalytic module, and simultaneously, a light source is started to carry out catalytic degradation reaction on the organic waste gas, wherein the volume airspeed of the organic waste gas is 40000h -1 。
Further, the method for identifying the performance degradation position of the dark catalytic material through the infrared thermal imaging graph comprises the following steps:
the infrared thermal imaging image of the dark catalytic material is acquired at regular time (every 30 minutes) through the FLIR GF309 infrared thermal imager, the irradiation intensity of the light source for the dark catalytic material is improved by a preset time (the preset time is every 5 minutes) before each acquisition of the infrared thermal imaging image (the light intensity of the light source is improved by 20%), and the irradiation intensity of the light source is reduced (the light intensity of the light source is reduced by 20%) after each acquisition of the image; converting each acquired thermal infrared image into a gray level image and detecting edges to obtain edges in the gray level image; dividing the gray image into a plurality of sections by each edge; selecting an interval of which the average gray value of each pixel in the interval is smaller than the average gray value of each pixel in the position of the interval corresponding to the infrared thermal imaging image acquired in the previous time, and marking the interval as an activity weakening position; and (3) recording the active weakening position with the maximum average gray value of each pixel in each active weakening position as a performance degradation position, wherein each infrared thermal imaging image corresponds to one performance degradation position.
Further, the method for calculating the deactivation strength of the dark catalytic material according to the performance degradation position comprises the following steps:
recording the acquisition times corresponding to the infrared thermal imaging graph as [1, N ] times, wherein N is the last acquisition time; recording the performance degradation position corresponding to the infrared thermal imaging image acquired for the nth time as LC (N); taking the performance degradation position with the minimum average gray value of each pixel in each performance degradation position as an anchor position; taking the performance degradation position with the maximum average gray value of each pixel in each performance degradation position as a target position; recording corresponding projection positions of the anchor position and the target position on a gray level image of an Nth acquired infrared thermal imaging image as an LC1 region and an LC2 region, taking a point with the largest difference value of gray level values in the anchor position and the LC1 region as an anchor point ancP1 and a point with the smallest difference value as an anchor point ancP2, and taking a point with the largest difference value of gray level values in the target position and the LC2 region as a target point tagP1 and a point with the smallest difference value as an anchor point tagP2; taking a quadrilateral area formed by four points of angP 1, tagP1, angP 2 and tagP2 as a performance-reducing transmission area;
taking the corresponding projection positions of the reduced performance transfer areas on all the infrared thermal imaging images as reduced performance transfer projection areas of each infrared thermal imaging image; forming a sequence of all performance-degrading positions in the performance-degrading transmission projection area according to the acquisition time sequence of the corresponding infrared thermal imaging image as a position queue, and sequentially calculating the inactivation intensity of each performance-degrading position;
the calculation method for calculating the inactivation intensity LoseStr (i) of the ith performance degradation position comprises the following steps: taking the average gray value of each point in the performance-reducing position as the performance gray, and recording the number of performance gray increase between every two performance gray in each performance gray from the 1 st performance-reducing position to the i th performance-reducing position in the position queue as UPN (i) and the number of performance gray decrease between every two performance gray as DON (i); loseStr (i) =upn (i)/(UPN (i) +don (i)) ×100.
The average deactivation intensity of the deactivation intensity of all performance-degrading sites is taken as the deactivation intensity of the dark catalytic material.
Where i is the sequence number of the degraded performance location in the location queue.
The method for controlling the light intensity in real time to ensure that the inactivation intensity of the dark catalytic material reaches a safe level comprises the following steps: when the deactivation intensity is greater than the set high threshold, the light intensity is controlled in real time to reduce the illumination intensity to the dark catalytic material until the deactivation intensity at the performance-degrading location of the newly acquired infrared thermal imaging map is reduced to a safe level.
Wherein the safety level is set to 20 as the value of the inactivation intensity, and the high-order threshold is set to 80 as the value of the inactivation intensity.
The method for controlling the light intensity in real time comprises the following steps:
when the current intensity Inten of the light source is Inten E (0.5 xBInt, 0.8 xBInt)]Then the current of the light source is reduced10% of the light intensity; when the current intensity Inten of the light source is Inten E (0.8×BInt, BInt)]Then the current intensity of the light source is reduced by 20%; wherein BInt is the maximum light intensity of the light source (the maximum light intensity is 1200mW/cm 2 ）。
The method for reducing the current light intensity of the light source comprises the following steps: the light source performs reduction adjustment on the light intensity through an ASL100-S4/16 intelligent lighting dimmer. The light source is a full spectrum solar light source.
Example 2
The calculation method for the inactivation strength LoseStr (i) in example 1 was replaced with:
let i be the serial number of the performance-degrading position in the position queue, record the maximum temperature value of each point in the ith performance-degrading position as SlowMax (i) and the minimum temperature value as SlowMin (i); within the range of i, marking an i-th reduced performance location and an i-1-th reduced performance location to produce reduced performance transfer between the i-th reduced performance location and the i-1-th reduced performance location if the i-th reduced performance location meets the conditions SlowMax (i-1) +overly (i-1, i) and SlowMin (i). Gtoreq.SlowMin (i-1) -overly (i-1, i);
wherein, the overlap (i) is the degradation transfer superposition value of the ith degradation position, and the calculation method is as follows:
；
PN is the number of performance-degrading positions in the position queue, j is a variable, and SMAx (i, j) is the difference between the maximum temperature value of each point in the ith performance-degrading position and the maximum temperature value of each point in the jth performance-degrading position; SMin (i, j) is the difference between the minimum temperature value for each point in the ith reduced performance location and the minimum temperature value for each point in the jth reduced performance location; smaxG (i, i-1) is the difference between the maximum temperature value for each point in the ith reduced performance location and the maximum temperature value for each point in the ith-1 reduced performance location; sminG (i, i-1) is the difference between the minimum temperature value for each point in the ith reduced performance location and the minimum temperature value for each point in the ith-1 reduced performance location;
the calculation method of the inactivation intensity LoseStr (i) for calculating the ith performance degradation position is as follows: taking the average gray value of each point in the performance-reducing positions as the performance gray, marking all adjacent two performance-reducing positions which generate performance-reducing transmission in all performance-reducing positions from 1 to i sequence numbers as transmission groups, counting the number of transmission groups with increased performance gray among all transmission groups as UPNumG (i), and counting the number of transmission groups with decreased performance gray among all transmission groups as DONumG (i);
the inactivation intensity LoseStr (i) =upnumgo (i)/(upnumgo (i) +donumo (i)) ×100; (the multiplication of 100 at the rear is to limit the value of the inactivation strength to between 0 and 100, and the inactivation strength is large when the value is large, whereas the inactivation strength is small).
The average deactivation intensity of the deactivation intensity of all performance-degrading sites is taken as the deactivation intensity of the dark catalytic material.
The step of controlling the light intensity in real time in example 1 to bring the deactivated intensity of the dark catalytic material to a safe level was replaced by: the temperature and the light intensity are controlled in real time so as to ensure that the inactivation strength of the dark catalytic material reaches a safe level, specifically: when the deactivation intensity is greater than the set high threshold, the light intensity and the temperature are controlled in real time to reduce the illumination intensity of the dark catalytic material and reduce the temperature of the catalytic module until the deactivation intensity of the performance-degrading position of the newly acquired infrared thermal imaging map is reduced to a safe level.
The method for controlling the light intensity in real time comprises the following steps:
when the current intensity Inten of the light source is Inten E (0.5 xBInt, 0.8 xBInt)]Then the current intensity of the light source is reduced by 10%; when the current intensity Inten of the light source is Inten E (0.8×BInt, BInt)]Then the current intensity of the light source is reduced by 20%; wherein BInt is the maximum light intensity of the light source (the maximum light intensity is 1200mW/cm 2 ）。
The method for controlling the temperature in real time comprises the following steps:
the temperature of the catalytic module is reduced by 10% when the temperature Temp of the catalytic module is Temp epsilon (0.5 XBTem, 0.8 XBTem), and by 20% when the temperature Temp of the catalytic module is Temp epsilon (0.8 XBTem, BTem), wherein BTem is a set temperature threshold (the temperature threshold is set to 300 ℃), wherein the method for reducing the temperature of the catalytic module is to refrigerate by a compression refrigerator.
Comparative example:
filtering the organic waste gas to be purified to remove particulate matters and viscous components to obtain dust-free waste gas;
adsorbing organic matters in the dust-free waste gas by using an adsorption material to obtain organic waste gas;
carrying out catalytic degradation reaction on the organic waste gas in a purification system to obtain purified gas;
the conditions of the purification system, the dark catalytic material, the light source, the organic waste gas to be purified and the like used in the comparative example are the same as those of examples 1 and 2.
Test results:
examples 1 and 2 and comparative examples were run on the same model of marine 180 heavy oil fuelled vessel, and after 24 months of running, the organic exhaust gas to be purified and the purified gas were checked and compared by gas chromatography, and the results showed that:
the purification efficiency of example 1 was greater than 95%, the purification efficiency of example 2 was greater than 90%, and the purification efficiency of example 3 was greater than 90% during 3 months of operation.
The purification efficiency of example 1 was greater than 92%, the purification efficiency of example 2 was greater than 90%, and the purification efficiency of example 3 was greater than 70% within 12 months of operation over 3 months.
The purification efficiency of example 1 was greater than 75%, the purification efficiency of example 2 was greater than 80%, and the purification efficiency of example 3 was greater than 50% within 24 months of operation over 12 months.
Dark catalytic materials of examples 1, 2 and comparative example after 24 months of operation were subjected to light intensity of 4000mW/cm for 30 minutes using USHIO UXM-Q256BY ultraviolet xenon lamp 2 Exciting the heat difference of each position of the dark catalytic material, and collecting infrared thermal imaging images of the dark catalytic materials of examples 1 and 2 and comparative examples by an FLIR GF309 infrared thermal imager; converting each acquired thermal infrared image into a gray level image and detecting edges to obtain edges in the gray level image; dividing the gray image into a plurality of sections by each edge; screening each of the intervalsThe area of the pixel with the smallest average gray value is respectively designated as an example 1 deactivated area, an example 1 deactivated area and a comparative example deactivated area (the area with the smallest average gray value indicates that the area has the lowest brightness in the thermal infrared image, i.e. the heat for exciting the dark catalytic material is the lowest, i.e. the dark catalytic material at the position is deactivated or is close to deactivated);
in the thermal infrared image, the area occupied by the deactivated region of example 1 was about 15%, the area occupied by the deactivated region of example 2 was about 6%, and the area occupied by the deactivated region of comparative example was about 42%. The larger the area therein means the larger the area where the dark catalytic material has been deactivated or is nearly deactivated.
It can be seen that examples 1 and 2 are greatly improved in service life and life of the catalyst under conditions of high temperature (170 ℃ C. To 500 ℃ C. In ship exhaust gas inlet temperature and exhaust gas outlet temperature), high oxidation environment, large air volume, long duration and severe steam, as compared with comparative examples, in which the dark catalytic material is lifted in ship exhaust gas.
In the present invention, an embodiment of a computer system is provided, and the embodiment is a system for treating exhaust gas of a photocatalytic ship, as shown in fig. 1, which is a system structure diagram of treating exhaust gas of a photocatalytic ship according to the present invention, and the system for treating exhaust gas of a photocatalytic ship of the embodiment includes: a processor, a memory and a computer program stored in the memory and executable on the processor, the processor implementing the steps in a system embodiment of a photo-thermal catalytic marine exhaust gas treatment as described above when the computer program is executed.
The system comprises: a memory, a processor, and a computer program stored in the memory and executable on the processor, the processor executing the computer program to run in units of the following system:
the thermal imaging acquisition unit is used for acquiring an infrared thermal imaging image of the dark catalytic material in the catalytic module;
the performance degradation identification unit is used for identifying the performance degradation position of the dark catalytic material through an infrared thermal imaging graph;
an inactivation strength calculation unit for calculating the inactivation strength of the dark catalytic material according to the performance degradation position;
and the dynamic control unit is used for controlling the temperature and/or the light intensity in real time so as to ensure that the deactivation intensity of the dark catalytic material reaches a safe level.
The system for treating the waste gas of the ship by photo-thermal catalysis can be operated in computing equipment such as a desktop computer, a notebook computer, a palm computer, a cloud server and the like. The system for photo-thermal catalytic ship exhaust gas treatment can comprise, but is not limited to, a processor and a memory. It will be appreciated by those skilled in the art that the examples are merely examples of one type of photo-thermal catalytic marine exhaust gas treatment system and are not limiting of one type of photo-thermal catalytic marine exhaust gas treatment system, and may include more or fewer components than examples, or may combine certain components, or different components, e.g., the one type of photo-thermal catalytic marine exhaust gas treatment system may also include input and output devices, network access devices, buses, etc.
The processor may be a central processing unit (CentralProcessingUnit, CPU), other general purpose processors, digital signal processors (DigitalSignalProcessor, DSP), application specific integrated circuits (ApplicationSpecificIntegratedCircuit, ASIC), field programmable gate arrays (Field-ProgrammableGateArray, FPGA) or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, or the like. The general purpose processor may be a microprocessor or the processor may be any conventional processor or the like, which is a control center of the system operation system for photo-thermal catalytic ship exhaust gas treatment, and various interfaces and lines are used to connect various parts of the entire system operation system for photo-thermal catalytic ship exhaust gas treatment.
The memory may be used to store the computer program and/or module, and the processor may implement various functions of the system for photo-thermal catalytic marine exhaust gas treatment by running or executing the computer program and/or module stored in the memory and invoking data stored in the memory. The memory may mainly include a storage program area and a storage data area, wherein the storage program area may store an operating system, an application program (such as a sound playing function, an image playing function, etc.) required for at least one function, and the like; the storage data area may store data (such as audio data, phonebook, etc.) created according to the use of the handset, etc. In addition, the memory may include high-speed random access memory, and may also include non-volatile memory, such as a hard disk, memory, plug-in hard disk, smart memory card (SmartMediaCard, SMC), secure digital (SecureDigital, SD) card, flash card (FlashCard), at least one magnetic disk storage device, flash memory device, or other volatile solid state storage device.
Although the present invention has been described in considerable detail and with particularity with respect to several described embodiments, it is not intended to be limited to any such detail or embodiment or any particular embodiment so as to effectively cover the intended scope of the invention. Furthermore, the foregoing description of the invention has been presented in its embodiments contemplated by the inventors for the purpose of providing a useful description, and for the purposes of providing a non-essential modification of the invention that may not be presently contemplated, may represent an equivalent modification of the invention.
What is not described in detail in the present specification belongs to the known technology of those skilled in the art.
Claims (4)
1. A method of photo-thermal catalytic marine exhaust gas treatment, the method comprising the steps of:
filtering the organic waste gas to be purified to remove particulate matters and viscous components to obtain dust-free waste gas;
adsorbing organic matters in the dust-free waste gas by using an adsorption material to obtain organic waste gas;
carrying out catalytic degradation reaction on the organic waste gas in a purification system to obtain purified gas;
during the catalytic degradation reaction, the catalytic module in the purification system is dynamically controlled in real time, and the specific method is as follows;
collecting an infrared thermal imaging image of a dark catalytic material in the catalytic module;
identifying performance degradation positions of the dark catalytic material through an infrared thermal imaging graph;
calculating the inactivation strength of the dark catalytic material according to the performance degradation position;
controlling the temperature and/or the light intensity in real time so as to ensure that the deactivation intensity of the dark catalytic material reaches a safe level;
the method for identifying the performance degradation position of the dark catalytic material through the infrared thermal imaging graph comprises the following steps: the method comprises the steps of regularly acquiring an infrared thermal imaging image of a dark catalytic material, improving the irradiation intensity of a light source for a preset time on the dark catalytic material before each acquisition of the infrared thermal imaging image, and reducing the irradiation intensity of the light source when each acquisition of the image is completed; converting each acquired thermal infrared image into a gray level image and detecting edges to obtain edges in the gray level image; dividing the gray image into a plurality of sections by each edge; selecting an interval of which the average gray value of each pixel in the interval is smaller than the average gray value of each pixel in the position of the interval corresponding to the infrared thermal imaging image acquired in the previous time, and marking the interval as an activity weakening position; the active weakening position with the maximum average gray value of each pixel in each active weakening position is marked as a performance degradation position, and each infrared thermal imaging image corresponds to one performance degradation position;
the method for calculating the inactivation strength of the dark catalytic material according to the performance degradation position comprises the following steps:
recording the acquisition times corresponding to the infrared thermal imaging graph as [1, N ] times, wherein N is the last acquisition time; recording the performance degradation position corresponding to the infrared thermal imaging image acquired for the nth time as LC (N); taking the performance degradation position with the minimum average gray value of each pixel in each performance degradation position as an anchor position; taking the performance degradation position with the maximum average gray value of each pixel in each performance degradation position as a target position;
recording corresponding projection positions of the anchor position and the target position on a gray level image of an Nth acquired infrared thermal imaging image as an LC1 region and an LC2 region, taking a point with the largest difference value of gray level values in the anchor position and the LC1 region as an anchor point ancP1 and a point with the smallest difference value as an anchor point ancP2, and taking a point with the largest difference value of gray level values in the target position and the LC2 region as a target point tagP1 and a point with the smallest difference value as an anchor point tagP2; taking a quadrilateral area formed by four points of angP 1, tagP1, angP 2 and tagP2 as a performance-reducing transmission area; taking the corresponding projection positions of the reduced performance transfer areas on all the infrared thermal imaging images as reduced performance transfer projection areas of each infrared thermal imaging image; forming a sequence according to the acquisition time sequence of the corresponding infrared thermal imaging diagram to serve as a position queue for all performance-reducing positions in the performance-reducing transmission projection area, sequentially calculating the inactivation intensity of each performance-reducing position, and taking the average inactivation intensity of the inactivation intensities of all the performance-reducing positions as the inactivation intensity of the dark catalytic material;
the calculation method for calculating the inactivation intensity LoseStr (i) of the ith performance degradation position comprises the following steps: taking the average gray value of each point in the performance-reducing position as the performance gray, and recording the number of performance gray increase between every two performance gray in each performance gray from the 1 st performance-reducing position to the i th performance-reducing position in the position queue as UPN (i) and the number of performance gray decrease between every two performance gray as DON (i); loseStr (i) =upn (i)/(UPN (i) +don (i)) ×100; wherein i is the sequence number of the performance-degrading position in the position queue;
the method for controlling the temperature and/or the light intensity in real time to ensure that the deactivation intensity of the dark catalytic material reaches a safe level comprises the following steps: when the deactivation intensity is greater than the set high threshold, the illumination intensity to the dark catalytic material is reduced and/or the temperature of the catalytic module is reduced until the deactivation intensity at the performance-degrading location of the newly acquired infrared thermal imaging map is reduced to a safe level.
2. A method of photo-thermal catalytic marine exhaust gas treatment according to claim 1, characterized in that the calculation method of the deactivation intensity LoseStr (i) for calculating the ith performance-degrading position is replaced by:
taking the average gray value of each point in the performance-reducing positions as the performance gray, marking all adjacent two performance-reducing positions which generate performance-reducing transmission in all performance-reducing positions from 1 to i sequence numbers as transmission groups, counting the number of transmission groups with increased performance gray among all transmission groups as UPNumG (i), and counting the number of transmission groups with decreased performance gray among all transmission groups as DONumG (i); the inactivation intensity LoseStr (i) =upnumgo (i)/(upnumgo (i) +donumo (i)) ×100.
3. A method of photo-thermal catalytic marine exhaust gas treatment according to claim 1, characterized in that the method of controlling the light intensity in real time is replaced by: when the current light intensity Inten of the light source is Inten epsilon (0.5 xBInt, 0.8 xBInt), the current light intensity of the light source is reduced by 10%, and when the current light intensity Inten of the light source is Inten epsilon (0.8 xBInt, BInt), the current light intensity of the light source is reduced by 20%, wherein BInt is the maximum light intensity of the light source.
4. A method of photo-thermal catalytic marine exhaust gas treatment according to claim 1, characterized in that the method of controlling the temperature in real time is replaced by: when the temperature Temp of the catalytic module is Temp epsilon (0.5 XBTem, 0.8 XBTem), the temperature of the catalytic module is reduced by 10%, and when the temperature Temp of the catalytic module is Temp epsilon (0.8 XBTem, BTem), the temperature of the catalytic module is reduced by 20%, wherein BTem is a set temperature threshold.
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| CN111111434A (en) * | 2020-01-15 | 2020-05-08 | 上海第二工业大学 | Equipment for catalytic degradation of VOCs gas through infrared heating |
| CN111203211A (en) * | 2020-02-28 | 2020-05-29 | 浙江大学 | Catalyst for photo-thermal synergistic plasma catalytic degradation of toluene and preparation method and application thereof |
| CN112316945A (en) * | 2020-11-03 | 2021-02-05 | 吉林大学 | Heterogeneous nano composite material, preparation method thereof, nitro reduction catalyst and application |
| CN115970738A (en) * | 2022-12-28 | 2023-04-18 | 上海第二工业大学 | Application of molecular sieve based catalyst based on waste lithium ion battery anode material in microwave catalytic oxidation of VOCs (volatile organic compounds) |
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