CN111693501A - Oil stain online monitoring method and device based on hydrophobic oil absorption material - Google Patents
Oil stain online monitoring method and device based on hydrophobic oil absorption material Download PDFInfo
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- CN111693501A CN111693501A CN202010572328.6A CN202010572328A CN111693501A CN 111693501 A CN111693501 A CN 111693501A CN 202010572328 A CN202010572328 A CN 202010572328A CN 111693501 A CN111693501 A CN 111693501A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
Abstract
The oil stain on-line monitoring method based on the hydrophobic oil absorption material comprises the following steps: (1) changing the oil stain types to obtain a time-varying curve of signal values of different oil stains under different using amounts; different oil stains have different signal value change slopes in the adsorption stage; (2) changing the temperature, and obtaining a change curve of fluorescence signal values of different oil stains under different usage conditions at different temperatures along with time according to the method in the step (1); (3) monitoring the change of signal value in the hydrophobic material on line, drawing the curve of the change of signal value with time, and comparing the signal value with V after the signal value is stable0And comparing, if the signal value changes, indicating that oil pollution exists, determining the type of the oil pollution according to the change slope of the signal value at the initial adsorption stage at the temperature, and matching the measured signal value change curve with the determined signal value change curve with time at different dosages of the oil pollution at the temperature to determine the content of the oil pollution. The invention also discloses a device for implementing the oil stain online monitoring method.
Description
Technical Field
The invention belongs to the field of monitoring of oil spilling of water bodies, and particularly relates to an oil stain online monitoring method and device.
Background
The ocean area accounts for about 71 percent of the total area of the earth, a large amount of petroleum resources are stored, the world economy and science and technology have been developed unprecedentedly since the 20 th century, the ocean is developed and utilized more and more by human beings, the ocean oil exploitation and transportation are continuously developed, the ocean oil spill pollution problem is more serious, the ocean environment is damaged inestimably, and the form is very severe.
Common and more traditional methods for monitoring marine oil spill include gravimetric methods, suspension methods and ultraviolet absorption methods. However, these methods require extraction, are complicated to operate, and cannot realize on-site on-line measurement. Other common online monitoring methods include dissolved oxygen monitoring, optical monitoring methods and the like, and the optical monitoring includes visible light monitoring, fluorescence technology, infrared technology, ultraviolet technology and the like. The visible light technology is economical and applicable, but has low discrimination, high false alarm rate and is also easily influenced by weather and climate; the infrared technology is easily interfered by phytoplankton and the like and is insensitive to thin oil films; ultraviolet is easy to affect atmospheric aerosol and ozone molecules by long-distance observation due to short wavelength and weak diffraction capability. In the oil spill detection, oil substances absorb light and can excite internal electrons under the irradiation of ultraviolet light due to the properties of fluorescent groups of the oil substances. The efficient and accurate acquisition and processing of the fluorescence signal are important links in the oil spill monitoring technology. However, the oil contamination monitoring is carried out by a remote sensing optical monitoring method, the monitoring period is long, and the initial oil spill accident can not be found in time. The dissolved oxygen monitoring method has the advantages that the oil spill pollution can be rapidly monitored, but the oxygen content is greatly influenced by the environment due to the monitoring factor, and the precision is not very high.
Disclosure of Invention
The invention overcomes the above determination in the prior art, provides an oil stain online monitoring method based on a hydrophobic oil absorption material and applying a fluorescence spectrum principle, and builds an oil stain online monitoring system for monitoring the change of the oil stain content in the hydrophobic oil absorption material in real time by using a newly developed optical sensor so as to realize the online monitoring of the offshore fixed point.
The invention is realized by the following technical scheme:
on one hand, the invention provides an oil stain online monitoring method based on a hydrophobic oil absorption material by applying a fluorescence method. The device adopts on-line monitoring, and an optical sensor in the on-line oil stain monitoring device comprises a cable device, a communication module, a control and data processing module, an information acquisition module and a detection device module; the cable device provides power for each module of each system and plays a role of circuit connection; the communication module is responsible for transmitting information transmitted by the connected front-end module; the excitation device module excites the oil stain fluorescence by irradiating the oil stain surface with light emitted by an LED lamp in the device, the fluorescence is reflected back to be received by the receiving plate and the received stray light is filtered, so that the fluorescence condition of the monitored sea surface is obtained; the excitation device module is mainly divided into an excitation device and a detection device; the information acquisition module cooperates with the detection device module, converts an analog signal transmitted by the detector into a digital signal, and records and stores the digital signal; the control and data processing module controls the modules to cooperatively move, effective information is acquired from the information acquisition module, digital signals are converted into fluorescence factor intensity signals through data processing, and the output fluorescence factor intensity signal value reflects relevant information of oil spilling.
The light-emitting end part of the optical sensor is fixed by the hydrophobic oil-absorbing material.
The invention only receives the fluorescence signal, converts the fluorescence signal into an analog signal, filters out the analog signals of clutter and reflected waves, and converts the analog signals into digital signals at the later stage to output the digital signals as fluorescence intensity.
The oil stain is firstly enriched by the hydrophobic oil absorption material fixed on the probe of the optical sensor, and then the probe of the optical sensor is monitored by the optical sensor, and the probe of the optical sensor is directly contacted with the oil stain, so that the response time is short.
The invention discloses an oil stain online monitoring method based on a hydrophobic oil absorption material, which comprises the following steps:
(1) placing the light-emitting end part of the optical sensor without the fixed hydrophobic oil absorption material in a simulated water body without oil stain at a set temperature, obtaining an initial signal value under the condition of no oil stain addition through the optical sensor, and recording a corresponding fluorescence intensity signal value I (a.u);
adding a certain amount of oil stain into an oil stain-free polluted water body, monitoring the change of a signal value of an optical sensor on line, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a signal value curve along with the change of time; and changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and recording until the signal value does not change along with the oil stain amount.
Changing the type of the oil stain, and obtaining a time-varying curve of signal values of different oil stains under different using amounts according to the method; different oil stains have different signal value change slopes in the adsorption stage.
Fixing a hydrophobic oil absorption material at a luminous end of an optical sensor, placing the luminous end of the optical sensor fixed with the hydrophobic oil absorption material in a simulated water body without oil stains at a fixed temperature, monitoring the change of a signal value in the hydrophobic oil absorption material on line according to the method, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a monitoring signal value along with the change of time; changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and indicating that the oil stain adsorption amount of the hydrophobic oil absorption material is saturated when the stable signal value is observed not to increase along with the increase of the oil stain amount any more; recording a time-varying curve of the signal value of the oil stain under different using amounts;
changing the type of the oil stain, and repeating the experiment according to the method to obtain a time-varying curve of the signal value of different oil stains under different using amounts; different oil stains have different signal value change slopes in the adsorption stage.
(2) Changing the temperature, and obtaining a change curve of fluorescence signal values of different oil stains under different usage conditions at different temperatures along with time according to the method in the step (1);
(3) fixingPlacing the light emitting end of the same optical sensor in the water body to be measured, monitoring the signal value change in the hydrophobic material on line, drawing a curve of the signal value changing along with time, and after the signal value is stable, combining the signal value with V0And comparing, if the signal value changes, indicating that oil pollution exists, determining the type of the oil pollution according to the change slope of the signal value at the initial adsorption stage at the temperature, and matching the measured signal value change curve with the determined signal value change curve with time at different dosages of the oil pollution at the temperature to determine the content of the oil pollution.
In the invention, the water type has no influence on the result.
In the invention, the hydrophobic oil absorption material can be a composite oil absorption cotton sheet, porous hydrophobic oil absorption fiber, hydrophobic oil absorption sponge, hydrophobic oil absorption felt and the like.
In the present invention, the oil contamination is derived from commercially available oils.
The sensor is used for monitoring oil spilling by utilizing a fluorescent spectrometry principle, the fluorescent spectrometry is used for exciting internal electrons to emit a fluorescence phenomenon by utilizing absorbed light energy of oil substances under the irradiation of ultraviolet light due to the property of fluorescent groups of the oil substances, and the unique fluorescent characteristics can be used as a distinguishing basis;
the optical sensor comprises a cable module, a communication module, a control and data processing module, an information acquisition module, a detection device module and an excitation device module.
The cable module provides corresponding driving power for different modules.
The communication module transmits the fluorescence information collected by the front end to the back end.
The detection device module comprises an excitation device and a receiving device, wherein the excitation device excites excitation light with specific wavelength, and the excitation wavelength is selected within the wavelength ranges of 300-; the receiving device receives fluorescence excited by the oil stain, receives the fluorescence signal and converts the fluorescence signal into a corresponding analog signal.
The information acquisition module comprises an A/D converter, reflected waves and other clutters are filtered out within the working effective time of the exciter, the fluorescence signal value of the monitored sea surface fluorescence spectrum is obtained, the analog signal received by the detector is converted into a digital signal, and the digital signal is transmitted to the control and data processing module.
The control and data processing module comprises an embedded micro-processing chip, processes the acquired fluorescence information, converts the digital signal into a fluorescence factor intensity signal, outputs a fluorescence factor intensity signal value reflecting the relevant information of the oil spill, judges whether the information is effective information of the oil spill, and then transmits the corresponding information to the control terminal (computer) through the communication module.
The terminal device comprises a computer and a server.
The optical sensor is of a closed structure as a whole.
The excitation device is an LED light source, and specific wavelength can be changed in the later stage according to different conditions.
The control and data processing module is used for data post-processing and analyzing and processing the obtained fluorescence factor intensity signal, and the model of the embedded micro-processing chip is preferably a single MSP43f149 chip.
Further, the signal transmission device may be a wired transmission device such as an optical fiber cable, a USB data cable, or a wireless transmission device such as a wireless transceiver, a microwave transmitter, or a satellite.
The device for implementing the oil stain online monitoring method based on the hydrophobic oil absorption material is characterized in that: including optical sensors, fiber optic cables, and server computers; the optical sensor transmits signals to the server computer through an optical fiber cable;
the detection device 2, the information acquisition module 8, the control and data processing module 11 and the communication module 13 which are connected by electric signals are sequentially arranged in the inner cavity of the shell of the optical sensor from the front end to the back end;
the detection device 2 comprises an excitation device 6 and a receiving device 3, wherein an LED lamp 7 in the excitation device 6 excites excitation light with a specific wavelength; the receiving device 3 receives fluorescence excited by oil stains, the receiving device 3 comprises a receiving plate 4 and a receiver 5, the receiving plate 4 filters received stray light within effective time, and the receiver 5 receives fluorescence signals and converts the fluorescence signals into corresponding analog signals; the front end of the shell 1 is provided with openings in the emitting direction of the LED lamp 7 and the incident direction of the receiving plate 4 for receiving the fluorescence;
the information acquisition module 8 comprises a clutter filtering module 9 and an A/D converter 10, acquires a fluorescence signal value of a monitored sea surface fluorescence spectrum, converts an analog signal received by the detector into a digital signal, and transmits the digital signal to the control and data processing module 11;
the control and data processing module 11 comprises an embedded micro-processing chip 12, processes the acquired fluorescence information, converts the digital signal into a fluorescence factor intensity signal, and reflects the relevant information of oil spill by the peak value of the output fluorescence factor intensity signal;
the communication module 13 comprises a communication front end 14 and a communication back end 16, and the fluorescent information signal collected by the communication front end 14 is transmitted to the communication back end 16 after being amplified and then transmitted to the server computer.
The working principle of the online oil spilling pollution monitoring device is that an exciting device in an exciting device module emits exciting light of the exciting device module to irradiate oil stains with fluorescence, the oil stains with fluorescence emit fluorescence under the action of the exciting light, and then a receiving device converts a fluorescence signal value into a corresponding analog signal; the converted analog signal is transmitted to the information acquisition module by the communication module, and the current analog signal is converted into a digital signal and stored. The data is transmitted to the control and data processing module, the digital information is converted into fluorescence factor intensity, the digital signal is converted into a fluorescence factor intensity signal, the output fluorescence factor intensity signal value reflects relevant information of oil spilling, the oil contamination degree of the water body to be detected is determined according to the fluorescence light intensity, and the oil contamination type of the water body to be detected is determined according to the fluorescence wavelength signal value.
The transmission method of the present invention may be wired transmission and wireless transmission, but is not limited thereto. The wireless transmission principle is as follows: the output signal value is compressed into digital signal, the information source redundancy is removed, the redundant information is introduced to resist channel noise and interference, different communication bodies are provided with different modulation methods, the coded digital (0, 1) sequence is changed into digital (or analog) baseband signal, then the baseband signal is frequency-modulated and amplified, and finally the signal is received by the satellite through antenna radiation.
In the present invention, the signal transmission may be wireless transmission, optical fiber transmission, satellite remote sensing transmission, etc., but is not limited thereto. The transmission principle of transmission through wireless signals is as follows: the method comprises the steps of compressing digital signals to monitored seawater fluorescence signal values, removing information source redundancy, introducing proper redundant information to resist channel noise and interference, changing coded digital (0, 1) sequences into digital (or analog) baseband signals according to different communication system differences according to different modulation methods, modulating the baseband signals to intermediate frequency for amplification, modulating the intermediate frequency signals to a radio frequency band, amplifying the radio frequency band, radiating the radio frequency band by an antenna, and enabling a satellite to receive the signals.
Compared with the prior art, the invention has the beneficial effects that:
1. the monitoring method is characterized in that a hydrophobic oil absorption material is added on the basis of an optical sensor, the enrichment is firstly carried out and then the monitoring is realized, a probe is directly contacted with the oil stain, the online monitoring can be rapidly and accurately carried out, and the method is suitable for the site fixed-point oil stain monitoring.
2. The monitoring method is based on the principle of laser-induced fluorescence, the laser has strong convergence and can be used under extreme conditions, the fluorescence emitted by the same sea level substance under different climatic conditions has wide consistency, the influence of the external environment can be avoided, and the monitoring method is not easily influenced by other targets.
3. The invention can realize simultaneous operation of on-site and remote monitoring, realize on-line unmanned monitoring and automatically acquire data for remote transmission.
4. The method can be used for monitoring the oil spill accidents in saline water and fresh water areas, is economical and has wide application prospect.
5. The optical sensor is an innovation point, can directly obtain the fluorescence intensity and wavelength to monitor the oil stain, and can monitor the oil stains with different pollution degrees and types according to the fluorescence intensity or the fluorescence wavelength of the oil stain.
Drawings
Fig. 1 is a schematic structural view of an optical sensor.
FIG. 2 is a graph showing the change of the voltage signal of the monitored engine oil with time by the optical sensor fixed with a layer of composite oil absorption cotton sheet.
FIG. 3 is a graph showing the change of the voltage signal of the monitored engine oil of the optical sensor with different fixed thickness composite oil absorption cotton sheets along with time.
FIG. 4 is a graph showing the change of the voltage signal of soybean oil monitored by an optical sensor fixed with a layer of composite oil absorbing cotton sheet along with time.
FIG. 5 is a graph showing the voltage signal of soybean oil monitored by an optical sensor with different thickness of composite oil-absorbing cotton sheets fixed along with the time.
FIG. 6 is a graph of the time-dependent change of the oil voltage signal monitored by the optical sensor under the shading condition.
FIG. 7 is a graph showing the change of the voltage signal of the monitored engine oil with time of the optical sensor with the composite oil absorption cotton sheets of different thicknesses fixed under the shading condition.
FIG. 8 is a graph showing the voltage signal of soybean oil monitored by an optical sensor with different thickness composite oil absorption cotton sheets fixed under a shading condition.
FIG. 9 is a time-dependent change curve of the voltage signal of the oil monitored by the optical sensor under the condition of the unfixed composite oil absorption cotton piece.
Fig. 10 is a schematic illustration of a hydrophobic oil absorbent material immobilized on an optical sensor.
Detailed Description
The invention is further illustrated with reference to the following examples, without limiting the scope of the invention thereto.
Example 1:
referring to the drawings, the parts are numbered as follows:
1. the device comprises a shell front end, a detection device, a receiving board, a receiver, a driving device, a light-emitting diode (LED) lamp, an information acquisition module, a clutter filter board, a light-emitting diode (A/D) converter, a control and data processing module, a micro-processing chip 12, an embedded micro-processing chip 13, a communication module 14, a communication front end, a cable 15, a cable 16, a communication rear end, a shell 17 and a hydrophobic oil absorption material 18.
The invention discloses an oil stain online monitoring method based on a hydrophobic oil absorption material, which comprises the following steps:
(1) placing the light-emitting end part of the optical sensor without the fixed hydrophobic oil absorption material in a simulated water body without oil stain at a set temperature, obtaining an initial signal value under the condition of no oil stain addition through the optical sensor, and recording a corresponding fluorescence intensity signal value I (a.u);
adding a certain amount of oil stain into an oil stain-free polluted water body, monitoring the change of a signal value of an optical sensor on line, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a signal value curve along with the change of time; and changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and recording until the signal value does not change along with the oil stain amount.
Changing the type of the oil stain, and obtaining a time-varying curve of signal values of different oil stains under different using amounts according to the method; different oil stains have different signal value change slopes in the adsorption stage.
Fixing a hydrophobic oil absorption material at a luminous end of an optical sensor, placing the luminous end of the optical sensor fixed with the hydrophobic oil absorption material in a simulated water body without oil stains at a fixed temperature, monitoring the change of a signal value in the hydrophobic oil absorption material on line according to the method, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a monitoring signal value along with the change of time; changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and indicating that the oil stain adsorption amount of the hydrophobic oil absorption material is saturated when the stable signal value is observed not to increase along with the increase of the oil stain amount any more; recording a time-varying curve of the signal value of the oil stain under different using amounts;
changing the type of the oil stain, and repeating the experiment according to the method to obtain a time-varying curve of the signal value of different oil stains under different using amounts; different oil stains have different signal value change slopes in the adsorption stage.
(2) Changing the temperature, and obtaining a change curve of fluorescence signal values of different oil stains under different usage conditions at different temperatures along with time according to the method in the step (1);
(3) fixing water body temperature, placing the light-emitting end of the same optical sensor in the water body to be measured, monitoring signal value change in the hydrophobic material on line, drawing a curve of signal value change along with time, and after the signal value is stable, making signal value and V be stable0And comparing, if the signal value changes, indicating that oil pollution exists, determining the type of the oil pollution according to the change slope of the signal value at the initial adsorption stage at the temperature, and matching the measured signal value change curve with the determined signal value change curve with time at different dosages of the oil pollution at the temperature to determine the content of the oil pollution.
Referring to the attached figure 1, the on-line oil stain monitoring device based on the hydrophobic oil absorption material comprises an optical sensor, an optical fiber cable and a server computer; the optical sensor transmits signals to the server computer through an optical fiber cable;
the optical sensor is composed of a shell 17, an LED lamp 7, a detection device module 2, a receiving device 3, a receiving plate 4, a receiver 5, an excitation device 6, an information acquisition module 8, a clutter filter plate 9, an A/D converter 10, a control and data processing module 11, an embedded micro-processing chip 12, a communication module 13, a communication front end 14, a cable 15, a communication rear end 16 and the shell 17 in the integrated shell 17.
The LED lamp 7 excites light within the wavelength ranges of 300-450nm and 450-600 nm;
the cable in the shell not only plays a role in information transmission, but also plays a role in power supply;
the front end 1 of the sensor shell is provided with an opening, and the opening direction is the same as the light source emitting direction of the LED lamp 7;
the detection device module 2 comprises an excitation device 6 and a receiving device 3, wherein an LED lamp 7 in the excitation device 6 excites excitation light with specific wavelength, and the excitation wavelength is selected within the wavelength ranges of 300-; the receiving device 3 receives fluorescence excited by oil stains, the receiving plate 4 filters the received stray light within an effective time, and the receiver 5 receives the fluorescence signals and converts the fluorescence signals into corresponding analog signals.
The information acquisition module 8 comprises an a/D converter 10, acquires a fluorescence signal value of the monitored sea surface fluorescence spectrum, converts an analog signal received by the detector into a digital signal, and transmits the digital signal to the control and data processing module 11.
The control and data processing module 11 comprises an embedded micro-processing chip 12, processes the acquired fluorescence information, converts the digital signal into a fluorescence factor intensity signal, and reflects the relevant information of oil spill by the peak value of the output fluorescence factor intensity signal; the communication module 13 amplifies the fluorescence information signal collected by the communication front end 14, transmits the amplified fluorescence information signal to the back end 16, and transmits the amplified fluorescence information signal to the control terminal (computer).
The terminal device comprises a computer and a server.
When in work: the LED lamp emits laser within a specified wavelength range, the laser irradiates oil stains with fluorescence, the oil stains emit fluorescence under the action of the laser, and a fluorescence signal is reflected, received by the receiving module, received by the receiving board and converted into an analog signal by the receiver; analog signals are transmitted to the information acquisition module through cables, an internal clutter filter plate simulates clutter and reflected waves, the filtered analog signals are converted into digital signals through an A/D converter, and the digital signals are transmitted to the control and data processing module through cables; the embedded micro-processing chip in the control and data processing module processes the acquired fluorescence information, converts a digital signal into a fluorescence factor intensity signal, transmits the fluorescence signal to the front end of the communication module through a cable, enhances the signal through a signal amplifier in the front end, and then transmits corresponding information to the control terminal through the front end of the information transmission module; and (4) obtaining the degree of the oil spill pollution in the seawater according to the fluorescent signal.
At room temperature, 1L of deionized water was placed in an experimental vessel, an optical sensor was fixed in a composite oil absorbent cotton sheet (purchased by Taobao, com/item), until the stability, the optical sensor after the stability is put into the water without vibration on the water surface, the fluorescence signal value is recorded and is kept stable, the vibration switch is turned on, the fluorescence signal value under the vibration water surface is recorded, 150mL of synthetic engine oil is added after the stability, ocean oil spill is simulated, the fluorescence signal change value is obtained through the optical sensor, the recorded signal value is drawn into a change curve, the signal value is found to be decreased in small amplitude and then raised suddenly after the engine oil is added, signal response is generated, the supplemented fluorescence signal value is increased from 41797a.u to 99817a.u, and the situation that a large amount of fluorescence is generated after oil contamination is added is shown in figure 2. This shows that the online monitoring of oil contamination in marine oil spill accidents can be realized by detecting the change of the oil contamination content in the hydrophobic oil absorption material through an optical sensor.
The fluorescence spectrum of the oil stain has identifiability as human fingerprints, can be used as a basis for identifying different oil stain types and determining the source and the type of oil spill, can reduce the possible range of the type of the oil spill, and can provide strong evidence support for oil spill monitoring. On the basis, the invention provides the optical sensor for monitoring different fluorescence intensities and fluorescence wavelengths of the marine oil spill to realize the on-line monitoring of the marine oil spill. The method has the advantages that the oil stain condition can be rapidly and accurately monitored according to the principle that the oil stain is enriched firstly and then monitored on the basis of the hydrophobic oil absorption material, the oil stain is in direct contact with the oil stain, the type of oil spill can be distinguished, the method is the only method which can distinguish the sea weed oil pollution and the detection of the sea beach oil spill at present, and the real-time on-line monitoring of the sea oil spill can be realized.
Example 2:
using the apparatus of example 1, seawater was simulated by adding 35g of sodium chloride (NaCl) to 1L of water at the same temperature; the experiment in example 1 was repeated to simulate an oil spill event, and the change in the fluorescence signal value of the optical sensor was monitored on-line by the sensor and plotted as a curve. The results are the same as in example 1, indicating that changing the type of water body has no effect on the response of the fluorescence signal value.
Example 3:
using the apparatus of example 1, diluted seawater was simulated by adding 35g of sodium chloride (NaCl) to 2L of water at the same temperature; the experiment in example 1 was repeated, the fluorescence signal value was monitored on-line by an optical sensor and a curve was drawn, and the results were the same as in example 1, and it was found that reducing the sodium chloride content did not have an effect on the experimental monitoring results.
Example 4:
the embodiment 4 is the same as the embodiment 1, except that the number of the circular composite oil absorption cotton sheets fixed at the luminous position of the sensor is changed into two layers or three layers. The signal value is recorded by the optical sensor and a curve is drawn, as shown in fig. 3, the change is exactly the same as that of the single-layer oil absorption cotton sheet, a large amount of fluorescence signals are generated after oil stains are added, but the signal value is not reduced like the single-layer oil absorption cotton sheet after being stabilized, which shows that the monitoring is more stable under the condition of fixing the composite oil absorption cotton sheets with two or three layers of thickness. This shows that different monitoring effects can be obtained by changing the thickness of the composite oil absorption cotton piece, namely the monitoring method of the invention can realize the monitoring of the oil stains of the oil absorption materials with different thicknesses.
Example 5:
example 5 same as example 1 except that the kind of oil was different, the kind of oil was changed to soybean oil (tuna soybean oil from a local store), as shown in fig. 4, and the result was that the fluorescence signal value decreased from 48742a.u to-149173 a.u after the oil was added, and gradually stabilized after reaching the lowest point of-198462 a.u and rising back to-163932 a.u with time, which indicates that the change of the kind of oil in the hydrophobic oil absorbent material can be detected by an optical sensor, and the present invention can realize the identification of the different kinds of oil.
Example 6:
the method of the embodiment 6 is the same as that of the embodiment 5, except that the number of the circular composite oil absorption cotton sheets fixed at the luminous position of the sensor is changed into two layers or three layers, the change of the fluorescence signal value is monitored on line through the sensor and is drawn into a curve, the fluorescence signal value is recorded after the fluorescence signal value is stable, as shown in fig. 5, the signal value is gradually stable, which shows that the change curves of the fluorescence signal values obtained by hydrophobic oil absorption materials with different thicknesses are different for different oil stains, and the method can realize the monitoring of the oil stains of the hydrophobic oil absorption materials with different oil stains and different thicknesses.
Example 7:
example 7a light-shielding device was added on the basis of example 1, and a fluorescence signal value was obtained on-line by an optical sensor and plotted as a change curve, as shown in fig. 6, it was found that the fluorescence signal value decreased by a small amount before it rose after the engine oil was added, a signal response was generated, the supplemented fluorescence signal value increased from 40661a.u to 79876a.u, the change trend was the same as that in example 1, which indicates that the illumination had little effect on the experimental results, and the present invention can implement on-line monitoring of oil contamination in an ocean oil spill accident in practical applications.
Example 8:
in the embodiment 8, the light shielding device is added on the basis of the embodiment 4, the fluorescence signal value is obtained on line through the optical sensor and is drawn into a change curve, as shown in fig. 7, it is found that the fluorescence signal value is decreased in a small amplitude and then rises suddenly after engine oil is added, signal response is generated, and the change trend is the same as that of the embodiment 4, which shows that the influence of illumination on the experimental result is small, and the invention can realize the online monitoring of oil contamination in the marine oil spill accident in practical application.
Example 9:
example 9 a light shielding device was added on the basis of example 6, as shown in fig. 8, the result showed that the change trend of the fluorescence signal value after the oil contamination was added was the same as that of example 6, which indicates that the illumination did not greatly affect the experimental result under the condition of different oil contamination types, and the present invention can realize the online monitoring of the oil contamination in the marine oil spill accident in practical application.
Example 10:
example 10 the same procedure as in example 1 was conducted except that the round composite oil absorbent cotton sheet was not fixed in this example. As shown in FIG. 9, the fluorescence signal value is increased from-81084 a.u to-67953 a.u after oil contamination is added, which shows that when the oil spill is detected by a sensor, the signal value is not obviously changed under the condition of no hydrophobic oil absorption material, so the hydrophobic oil absorption material is indispensable for constructing an online oil contamination monitoring system in an ocean oil spill accident.
Claims (3)
1. The oil stain on-line monitoring method based on the hydrophobic oil absorption material comprises the following steps:
(1) placing the light-emitting end part of the optical sensor without the fixed hydrophobic oil absorption material in a simulated water body without oil stain at a set temperature, obtaining an initial signal value under the condition of no oil stain addition through the optical sensor, and recording a corresponding fluorescence intensity signal value I (a.u);
adding a certain amount of oil stain into an oil stain-free polluted water body, monitoring the change of a signal value of an optical sensor on line, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a signal value curve along with the change of time; changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and recording until the signal value does not change along with the oil stain amount;
changing the type of the oil stain, and obtaining a time-varying curve of signal values of different oil stains under different using amounts according to the method; different oil stains have different signal value change slopes in the adsorption stage;
fixing a hydrophobic oil absorption material at a luminous end of an optical sensor, placing the luminous end of the optical sensor fixed with the hydrophobic oil absorption material in a simulated water body without oil stains at a fixed temperature, monitoring the change of a signal value in the hydrophobic oil absorption material on line according to the method, enabling the signal value to tend to be stable along with the change of time, recording the stable signal value, and drawing a monitoring signal value along with the change of time; changing the amount of the added oil stain, recording a stable signal value, drawing a monitoring signal value curve changing along with time, and indicating that the oil stain adsorption amount of the hydrophobic oil absorption material is saturated when the stable signal value is observed not to increase along with the increase of the oil stain amount any more; recording a time-varying curve of the signal value of the oil stain under different using amounts;
changing the type of the oil stain, and repeating the experiment according to the method to obtain a time-varying curve of the signal value of different oil stains under different using amounts; different oil stains have different signal value change slopes in the adsorption stage;
(2) changing the temperature, and obtaining a change curve of fluorescence signal values of different oil stains under different usage conditions at different temperatures along with time according to the method in the step (1);
(3) fixing water body temperature, placing the light-emitting end of the same optical sensor in the water body to be measured, monitoring signal value change in the hydrophobic material on line, drawing a curve of signal value change along with time, and after the signal value is stable, making signal value and V be stable(0)And comparing, if the signal value changes, indicating that oil pollution exists, determining the type of the oil pollution according to the change slope of the signal value at the initial adsorption stage at the temperature, and matching the measured signal value change curve with the determined signal value change curve with time at different dosages of the oil pollution at the temperature to determine the content of the oil pollution.
2. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 1, characterized in that: the hydrophobic oil absorption material is a composite oil absorption cotton sheet, porous hydrophobic oil absorption fibers, hydrophobic oil absorption sponge or hydrophobic oil absorption felt.
3. The device for implementing the oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 1, is characterized in that: including optical sensors, fiber optic cables, and server computers; the optical sensor transmits signals to the server computer through an optical fiber cable;
a detection device (2), an information acquisition module (8), a control and data processing module (11) and a communication module (13) which are connected by electric signals are sequentially arranged in the inner cavity of the shell of the optical sensor from the front end to the back end;
the detection device (2) comprises an excitation device (6) and a receiving device (3), wherein an LED lamp (7) in the excitation device (6) excites excitation light with a specific wavelength; the receiving device (3) receives fluorescence excited by oil stains, the receiving device (3) comprises a receiving board (4) and a receiver (5), the receiving board (4) filters received stray light within effective time, and the receiver (5) receives and converts a fluorescence signal into a corresponding analog signal; the front end of the shell (1) is provided with openings in the emitting direction of the LED lamp (7) and the incident direction of the receiving plate (4) for receiving the fluorescence;
the information acquisition module (8) comprises a clutter filtering module (9) and an A/D converter (10), acquires a fluorescence signal value of a monitored sea surface fluorescence spectrum, converts an analog signal received by the detector into a digital signal, and transmits the digital signal to the control and data processing module (11);
the control and data processing module (11) comprises an embedded micro-processing chip (12), the acquired fluorescence information is processed, the digital signal is converted into a fluorescence factor intensity signal, and the peak value of the output fluorescence factor intensity signal reflects the relevant information of oil spilling;
the communication module (13) comprises a communication front end (14) and a communication back end (16), and the fluorescence information signals collected by the communication front end (14) are transmitted to the communication back end (16) after being enhanced and amplified and then transmitted to the server computer.
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| CN202010572328.6A CN111693501A (en) | 2020-06-22 | 2020-06-22 | Oil stain online monitoring method and device based on hydrophobic oil absorption material |
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| CN202010572328.6A CN111693501A (en) | 2020-06-22 | 2020-06-22 | Oil stain online monitoring method and device based on hydrophobic oil absorption material |
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