CN110231374B - Oil stain online monitoring method based on hydrophobic oil absorption material - Google Patents
Oil stain online monitoring method based on hydrophobic oil absorption material Download PDFInfo
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- CN110231374B CN110231374B CN201910575591.8A CN201910575591A CN110231374B CN 110231374 B CN110231374 B CN 110231374B CN 201910575591 A CN201910575591 A CN 201910575591A CN 110231374 B CN110231374 B CN 110231374B
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses an oil stain online monitoring method based on a hydrophobic oil absorption material, which adopts a device comprising a signal acquisition device, a signal transmission device and a signal processing device, wherein the signal acquisition and measurement device consists of 1 or more oxygen sensors and the hydrophobic oil absorption material, and the probe part of the oxygen sensor is fixed in the hydrophobic oil absorption material; the method comprises the following steps: (1) under the set temperature, obtaining the voltage signal value change curve of different oil stains under the condition of different using amounts along with time; (2) changing the temperature, and obtaining voltage signal value time-varying curves of different oil stains under different consumption conditions at different temperatures according to the method in the step (1); (3) and (3) measuring the temperature of the water body to be measured, placing the same signal acquisition device in the water body to be measured, obtaining a curve of the voltage signal value changing along with time, and determining the oil stain type and the oil stain content through curve matching. The invention can realize the on-line monitoring of oil contamination in fresh water or ocean oil spill accidents.
Description
Technical Field
The invention belongs to the field of monitoring of oil stains in water bodies, and particularly relates to an oil stain online monitoring method based on a hydrophobic oil absorption material.
Background
The ocean oil spill pollution is one of various ocean pollutions with the widest influence range, the longest harm time and the largest damage to the ecological environment. The method has great significance for treating marine oil spill pollution by quickly, accurately and online detecting oil stains in real time to feed back the specific conditions of an oil spill area, and can reduce the adverse effect of oil spill on the environment to the maximum extent.
The conventional methods for monitoring oil spill pollution mainly comprise a hyperspectral technique, an infrared/ultraviolet absorption spectroscopy, a laser fluorescence method, a microwave radiation method, a microwave scattering method, radar remote sensing and the like, and the methods mainly measure spectral characteristics (reflectivity, fluorescence characteristics and scattering spectrum) of oil stains on the water surface under the irradiation of light rays of different wave bands, and perform data processing and analysis after receiving response signals through a sensor or a radar so as to give the oil film thickness or the oil spill amount. The monitoring methods are easily influenced by factors such as data processing precision, geographical environment and the like when oil film spectrum data of oil spilled on an actual water surface are measured, so that the oil film identification precision is low, and data related to oil film thickness characteristics are difficult to obtain. Therefore, in order to further guarantee the guiding effect of the oil spill monitoring result on the actual oil pollution treatment, the development of a novel sea surface oil spill monitoring method is urgent, so that the monitoring capability of the water surface oil spill is practically improved.
Oxygen content plays an extremely important role in marine environmental monitoring, and oxygen sensors are increasingly widely applied. Based on the fact that after the hydrophobic oil absorption material absorbs oil, the oxygen content in the oil absorption material has a certain internal relation with the type and the oil stain amount of oil stains, the invention provides that the change of the oxygen content in the hydrophobic oil absorption material is detected through an oxygen sensor to realize the online monitoring of the oil stains in the ocean oil spill accident. The invention has the advantages of fixed-point real-time on-line monitoring, high accuracy, difficult interference by false targets and guiding function on actual oil pollution treatment.
Disclosure of Invention
Aiming at the problem of oil pollution in water body oil spill accidents, the invention aims to provide an oil pollution online monitoring method based on a hydrophobic oil absorption material, which realizes the online monitoring of oil pollution in fresh water or ocean oil spill accidents by monitoring the change of the oxygen content in the hydrophobic oil absorption material in real time through an oxygen sensor.
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, which adopts an online oil stain monitoring device to perform online monitoring, wherein the online oil stain monitoring device comprises a signal acquisition device, a signal transmission device and a signal processing device; the signal acquisition device transmits signals to the signal processing device through the signal transmission device; the signal acquisition and measurement device consists of 1 or more oxygen sensors and a hydrophobic oil absorption material, wherein the probe part of the oxygen sensor is fixed in the hydrophobic oil absorption material;
the oil stain online monitoring method comprises the following steps:
(1) under the set temperature, the signal acquisition device is arranged in the water body without oil pollution, the initial oxygen content in the hydrophobic oil absorption material under the condition of no oil pollution is obtained through the oxygen sensor, and the corresponding voltage signal value V at the moment is recorded0；
Adding oil stains into a water body without oil stains, monitoring the change of oxygen content in the hydrophobic oil absorption material on line, drawing a curve of voltage signal values changing along with time, enabling the voltage signal values changing along with time to be stable, and recording the stable voltage signal values; changing the amount of the added oil stain, drawing a curve of the voltage signal value changing along with time, and recording a stable voltage signal value, wherein when the stable voltage signal value is observed not to increase along with the increase of the oil stain amount any more, the oil stain adsorption amount of the monitoring device is saturated at the moment; storing the voltage signal value time-varying curves of the oil stain under different dosage conditions, wherein the curves have the same voltage signal value rising slope at the initial adsorption stage;
changing the category of the oil stains, and obtaining a voltage signal value time-varying curve of different oil stains under different using amounts according to the method; different oil stains have different voltage signal value rising slopes at the initial adsorption stage;
(2) changing the temperature, and obtaining voltage signal value time-varying curves of different oil stains under different consumption conditions at different temperatures according to the method in the step (1);
(3) measuring the temperature of the water body to be measured, placing the same signal acquisition device in the water body to be measured, monitoring the change of the oxygen content in the hydrophobic oil absorption material on line, and drawing a voltage signal valueFrom the voltage signal value and V after the voltage signal value is stabilized by the time-varying curve0The oil pollution condition of the water body to be detected is obtained through the numerical value change, if the voltage signal value is increased, the oil pollution is shown, the oil pollution category is determined according to the rising slope of the voltage signal value of the adsorption initial stage at the temperature, and then the time change curve of the voltage signal value of the water body to be detected is matched with the time change curve of the voltage signal value of the determined oil pollution under the condition that the oil pollution does not use the amount at the temperature so as to determine the oil pollution content.
In the invention, the type of the water body has no influence on the response of the voltage signal value.
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 invention, the position of the signal acquisition device in the water body has almost no influence on the monitoring result.
In the invention, the oil pollution is from light crude oil, medium crude oil, extra heavy crude oil, petroleum ether, carbon tetrachloride, gasoline, synthetic engine oil and the like.
In the present invention, the oxygen sensor may be a non-oxygen consuming optical oxygen sensor, an electrochemical oxygen consuming oxygen sensor, a portable oxygen sensor, etc. based on the principle of fluorescence quenching, and preferably an optical fiber oxygen sensor capable of realizing on-line monitoring.
Preferably, the optical fiber oxygen sensor is detachably connected with the sensor main body part and the probe part; the sensor main body part consists of a hollow shell, a blue light source, a red light source, a light source driver, a conducting optical fiber, a fluorescence receiving plate, a red light filter, a photoelectric sensing device, a signal acquisition card, a signal identifier and a control circuit board, wherein the blue light source and the red light source are integrated in the shell; the probe part consists of a cover body matched with the shell and an oxygen sensitive layer which is integrated in the cover body and can excite fluorescence; the cover body is provided with a through hole, and an optical isolation layer which can permeate oxygen is arranged at the through hole; the optical isolation layer in the cover body is sequentially provided with an oxygen sensitive layer and a transparent carrier sheet from bottom to top;
the LED light source is in driving connection with the light source;
the end of the shell close to the cover body is provided with an opening, the direction of the opening is the same as the emitting direction of the LED light source, and a channel for emitting light or reflecting light of the LED light source is formed and used for guiding the emitting light to the oxygen sensitive layer;
the fluorescence receiving plate guides the fluorescence emitted by the oxygen sensitive layer to the photoelectric sensing device, a red light filter is arranged at the light inlet end of the photoelectric sensing device, and the photoelectric sensing device is connected with the receiving end of the conducting optical fiber;
the signal acquisition card is connected with the conductive rear end of the conductive optical fiber and is stored in the signal identifier;
the light source driving and photoelectric sensing device and the signal identifier are respectively electrically connected with the control circuit board;
the whole optical fiber oxygen sensor is of a closed structure.
The optical fiber oxygen sensor is connected with the signal transmission device and the signal processing device in sequence.
The LED light source is preferably blue light with the wavelength of 475nm and red light with the wavelength of 600nm, and the blue light can excite the red light to be reflected and then converted into an electric signal through a photoelectric sensor to serve as a reference signal, so that the influence caused by environmental factors is eliminated.
Further, the sensor body part and the probe part can be connected through threads or a snap connection.
Further, the optical isolation layer is preferably silicone, and the oxygen-sensitive layer is preferably an oxygen-sensitive fluorescent film containing an oxygen-sensitive fluorescent indicator tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride.
The signal acquisition card is used for acquiring the condition of each monitored part in real time and storing the condition in the signal recognizer for standby reading in real time.
The signal recognizer of the invention is used for polling each signal acquisition card in a fixed time period, reading data stored in the signal acquisition card, and transmitting the status data of each monitored part to the control circuit board through A/D conversion of the data transmission interface.
The control circuit board is used for signal acquisition and signal conversion, and the model of the control circuit board is preferably a single MSP43f149 chip, and the control circuit board comprises: the control unit module is connected with the transmitting unit module and the data processing module and is used for controlling the transmitting unit module and the data processing module; the input end of the transmitting unit module is connected with the control unit module, and the output end of the transmitting unit module is connected with the light source for driving; the data processing module receives the electric signal which is transmitted by the photoelectric sensor and reflects the fluorescence intensity and directly sends out the electric signal, or the electric signal which reflects the fluorescence intensity is converted into wireless data through a signal converter and then is sent out.
Furthermore, the signal transmission device is an optical fiber cable, a USB data line, a wireless transceiver, a microwave transmitter or a satellite.
Further, the signal processing device is a server computer, a microwave receiver or a data processor.
The working principle of the online oil spilling pollution monitoring device is that a blue LED light source and a red LED light source are driven by the light sources to emit blue light and red light to irradiate an oxygen sensitive fluorescent film containing an oxygen sensitive fluorescent indicator under the control of a control circuit board, the oxygen sensitive fluorescent film containing the oxygen sensitive fluorescent indicator emits fluorescence under the action of the blue light, a fluorescent signal is received by a fluorescent receiving board through reflection and is converted into an electric signal through a photoelectric sensor provided with a red light optical filter, and simultaneously the red light emitted by the red LED lamp is converted into the electric signal through the photoelectric sensor through reflection to serve as a reference signal; the signal is filtered by the photoelectric sensor and then transmitted to the information acquisition card by the conducting fiber, and the information recognizer inspects each signal acquisition card in a fixed time period, reads the data stored in the card, and transmits the status data of each monitored part to the control circuit board by the A/D conversion of the data transmission interface; and the signal request reaching the control circuit board is transmitted to the signal processing device through the signal transmission device, and the petroleum pollution degree in the seawater is obtained according to the corresponding relation between the fluorescence intensity and the oxygen content concentration in the oil spilling pollution area.
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 a monitored seawater voltage signal value, removing information source redundancy, introducing proper redundant information to resist channel noise and interference, changing a coded digital (0, 1) sequence into a digital (or analog) baseband signal according to different communication system differences according to different modulation methods, modulating the baseband signal to an intermediate frequency for amplification, modulating the intermediate frequency signal to a radio frequency band, amplifying the signal, radiating the signal through an antenna, and enabling a satellite to receive the signal.
Compared with the prior art, the invention has the beneficial effects that:
1. the monitoring method of the invention realizes the online monitoring of the oil stain in the ocean oil spill accident by detecting the change of the oxygen content in the hydrophobic oil absorption material through the oxygen sensor, has accurate and reliable monitoring data of the oxygen content and fast response, and is suitable for the fixed-point real-time online oil stain monitoring;
2. the monitoring method is not influenced by external factors such as marine environment, meteorological conditions and the like, is not easily interfered by false targets, and can quickly and accurately monitor the type and the oil spilling amount of the oil stains in the oil spilling accident.
3. The invention can observe the measurement result on site, realize long-term online unmanned monitoring through a remote communication interface, and realize automatic acquisition and transmission of data.
4. The invention can be widely applied to monitoring oil spill accidents in areas such as seawater, lake water and the like, has low cost and has wide application prospect.
Drawings
FIG. 1 is a graph showing the variation of the on-line voltage signal obtained by the optical fiber oxygen sensor
FIG. 2 is a graph of voltage signal value of the optical fiber oxygen sensor as a function of oil contamination amount;
FIG. 3 is a graph of voltage signal values over time for different classes of oil stains;
FIG. 4 is a graph of the effect of different types of oil absorbing materials on the value of the oxygen sensor voltage signal;
FIG. 5 is an illustration of the effect of the fixed position of the probe of the oxygen sensor in the oil absorbent material on the value of the voltage signal;
FIG. 6 is an illustration of the effect of oxygen sensor type on voltage signal value;
fig. 7 is an oil contamination online monitoring device based on a hydrophobic oil absorption material.
FIG. 8 is a schematic diagram of the general structure of a fiber optic oxygen sensor;
FIG. 9 is a detailed schematic diagram of a fiber optic probe of the oxygen sensor;
FIG. 10 is a top view of a fiber optic probe of the oxygen sensor;
FIG. 11 is a schematic structural diagram of an optical fiber body of an oxygen sensor;
FIG. 12 is a front view of a fiber optic probe of the oxygen sensor;
fig. 13 is a rear view of the optical fiber probe of the oxygen sensor.
The device comprises a shell 1, a shell 2, a fluorescence receiving plate 3, a light source drive 4, a conducting optical fiber 5, a red light filter 6, a blue light filter 7, a photoelectric sensing device 8, a signal acquisition card 9, a signal recognizer 10, a control circuit board 11, a cover body 12, a through hole 13, an optical isolation layer 14, an oxygen sensitive layer 15, a transparent carrier sheet 16, a blue LED lamp 17, a red LED lamp 18, an optical fiber oxygen sensor 19, a hydrophobic oil absorption material 20, an optical fiber cable 21 and a server computer.
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 fig. 7-13, an on-line oil contamination monitoring device is shown in fig. 7, and includes a signal acquisition device, an optical fiber cable 20 and a server computer 21; the signal acquisition device transmits signals to the server computer through an optical fiber cable;
the signal acquisition device consists of 4 optical fiber oxygen sensors 18 and a composite oil absorption cotton sheet, wherein the probe part of the optical fiber oxygen sensor 18 is fixed in the composite oil absorption cotton sheet; the optical fiber oxygen sensor 18 is formed by connecting a sensor main body part and a probe part through threads; the whole optical fiber oxygen sensor 18 is of a closed structure;
the sensor main body consists of a hollow shell 1, a blue LED lamp 16, a red LED17, a light source driver 3, a conducting optical fiber 4, a red light filter 5, a blue light filter 6, a photoelectric sensor 7, a signal acquisition card 8, a signal identifier 9 and a control circuit board 10, wherein the blue LED lamp 16 and the red LED17 are integrated in the shell 1; the probe part consists of a cover body 11 matched with the shell body 1 and an oxygen-sensitive fluorescent film which is integrated in the cover body 11 and can excite fluorescence and contains an oxygen-sensitive fluorescent indicator (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride; a through hole is arranged on the cover body 12, and silicone is arranged at the through hole; an oxygen-sensitive fluorescent film containing an oxygen-sensitive fluorescent indicator tri (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride and a transparent carrier sheet 15 are sequentially arranged on the silicone inside the cover body 12 from bottom to top;
the blue LED lamp 16 is provided with a blue light filter which can emit blue light of 450 nm;
the blue LED lamp 16 and the red LED lamp 17 are respectively and electrically connected with the light source driver 3;
an opening is formed in the end, close to the cover body 11, of the shell body 1, the opening direction is the same as the emitting direction of the LED light source, a channel for emitting blue light by the blue LED light source 2 and emitting red light by the red LED lamp is formed, and the channel is used for guiding the emitted light to the oxygen-sensitive fluorescent film containing the oxygen-sensitive fluorescent indicator;
the fluorescence receiving plate 5 guides the fluorescence emitted by the oxygen-sensitive fluorescent film containing the oxygen-sensitive fluorescent indicator to the photoelectric sensor part 7, a red light filter 5 is arranged at the light inlet end of the photoelectric sensor part 7, and the photoelectric sensor part 7 is connected with the receiving end of the conducting optical fiber 4;
the signal acquisition card 8 is connected with the conductive rear end of the conductive optical fiber 4, and the signal acquisition card 8 is stored in the signal identifier 9;
the light source driver 3, the photoelectric sensing device and the signal identifier 7 are respectively electrically connected with the control circuit board 10;
the control circuit board 10 is responsible for acquisition of fluorescent signals, concentration calculation and data storage, is the core of the whole control, and is responsible for command sending, data acquisition and data processing and is connected with a server computer through an optical fiber cable; the control circuit board adopts an MSP43f149 single chip microcomputer, and comprises: the device comprises a control unit module, a transmitting unit module and a data processing module; the control unit module is respectively connected with the transmitting unit module and the data processing module; the data processing module receives an electric signal which reflects the fluorescence intensity and is transmitted by the photoelectric sensing device, the input end of the transmitting unit module is connected with the control unit module, and the output end of the transmitting unit module is connected with the light source drive and is used for controlling the work of the LED light source; the input end of the data processing module is used for receiving an electric signal generated by the photoelectric sensor, the output end of the data processing module is connected with the server computer through an optical fiber cable to realize communication, and the data processing module judges the ocean oil spill pollution condition according to the collected data.
When in work: the blue LED light source and the red LED light source are driven by the light source to emit blue light and red light to irradiate on the oxygen-sensitive fluorescent film containing the oxygen-sensitive fluorescent indicator under the control of the control circuit board, the oxygen-sensitive fluorescent film containing the oxygen-sensitive fluorescent indicator emits fluorescence under the action of the blue light, a fluorescent signal is received by the fluorescent receiving board after being reflected, and is converted into an electric signal through the photoelectric sensor provided with the optical filter of the red light, and meanwhile, the red light emitted by the red LED lamp is reflected and is converted into the electric signal through the photoelectric sensor to serve as a reference signal; the signal is filtered by the photoelectric sensor and then transmitted to the information acquisition card by the conducting fiber, and the information recognizer inspects each signal acquisition card in a fixed time period, reads the data stored in the card, and transmits the status data of each monitored part to the control circuit board by the A/D conversion of the data transmission interface; the signal request reaching the control circuit board is transmitted to the server computer 21 through the optical fiber transmission cable 20, and the petroleum pollution degree in the seawater is obtained according to the corresponding relation between the fluorescence intensity and the oxygen content concentration in the oil spilling pollution area.
At 25 ℃, 1000ml of deionized water was taken, and the probe of the fiber oxygen sensor was fixed on a hydrophobic circular composite oil absorbent cotton piece (purchased by Taobao, with the purchase link: https:// item. taobao.com/item. htmut _ sk ═ 1.XD34xu/0bsEDAIers3cOsu4p _21380790_ 156161466985. copy.1& id ═ 537317434400& sourceType ═ 124& suc &. 1EB70A76-AABC-4D 4-A-9994-F3D 4D497C9C2& un ═ 02157 4F 71b33e 5 bb998F85& share _ v & _ 2& gt, 5 # 2& ksherein wf10. fw _ 5 # 3 g & @ 240) was taken at 25) was taken at 25.240 g & 5 the water surface of the water was taken at 25.240, the water was taken) was taken at 25.240, the water surface of the water was taken as the devices was taken on the water was taken as the water surface of the water and the device was measured and the water was measured and the device was taken as a sample was taken at 25.240 g.240, the water surface of the water was taken and the water was measured and the sample was measured by a sample was taken from the sample was taken and the sample was measured and the sample was taken by a sample was taken and. Subsequently, 20mL of synthetic motor oil was added to the deionized water to simulate an oil spill event, a slight shaking was performed, the voltage signal values were obtained online via a fiber optic oxygen sensor and plotted as a change curve, and it was found that the voltage signal values slowly increased after the addition of motor oil to produce a signal response, increasing the supplemental voltage signal values from 98078a.u to 109613a.u, see fig. 1. This shows that the online monitoring of oil contamination in the marine oil spill accident can be realized by detecting the change of the oxygen content in the hydrophobic oil absorption material through the oxygen sensor.
Example 2:
using the apparatus of example 1, 35g of sodium chloride (NaCl) was added to 1000mL of water at 25 ℃, and stirred with a glass rod to be uniformly dissolved, to obtain simulated seawater; placing the signal acquisition device in simulated seawater; and adding 20mL of synthetic engine oil into the simulated seawater, simulating an oil spill event, slightly shaking, monitoring the change of a voltage signal value of the oxygen sensor on line through the optical fiber oxygen sensor, and drawing a curve. The results are the same as in example 1, which indicates that changing the type of water body has no effect on the response of the voltage signal value.
Example 3:
using the apparatus of example 1, 35g of sodium chloride (NaCl) was added to 2000mL of water at 25 ℃, and stirred with a glass rod to dissolve it uniformly, to obtain a dilute concentration of simulated seawater; placing a signal acquisition device in simulated seawater with west concentration; and then adding 20mL of synthetic engine oil into the simulated seawater to simulate an oil spill event, slightly shaking, monitoring a voltage signal value on line through an optical fiber oxygen sensor and drawing a curve, wherein the result is the same as that in the example 1, and the effect of reducing the content of sodium chloride on the experimental monitoring result is found to be not influenced.
Example 4:
example 4 is the same as example 2 except that the amounts of the added synthesizer oil were 5mL, 10mL and 15mL, the changes in the voltage signal values were monitored on-line by the optical fiber oxygen sensor and plotted as curves, the voltage signal values were recorded after the voltage signal values were stabilized, and a graph of the relationship between the stabilized voltage signal values and the usage amount of the synthesizer oil was plotted, as shown in fig. 2, it was found that the amounts of the added synthesizer oil were different and the stabilized voltage signal values of the optical fiber oxygen sensor were different, but the rising slopes of the voltage signal values at 0 to 100s of these curves were substantially the same.
Example 5:
example 5 the same procedure as in example 2, except that CCl was used as the oil-based substance4The voltage signal values continuously obtained by the optical fiber oxygen sensor are drawn into curves, as shown in fig. 3, it is found that at 50s, the change curves of the voltage signals have different change trends along with different oil stain types, which shows that the change of the oil type has obvious influence on the measurement result, namely, the monitoring method of the invention can realize the identification of the oil stain types.
Example 6:
the method of example 6 is the same as that of example 2, except that the types of the hydrophobic oil absorption materials are different, the monitoring results of the oil absorption materials are porous super-hydrophobic oil absorption fibers (from Ningbo materials) and super-hydrophobic oil absorption sponges (from high polymer materials and engineering research and development rooms at the institute of Jiang, university of Zhejiang Industrial university) are shown in fig. 4, and the results show that the types of the used oil absorption materials are different, and the obtained voltage signal value change curves of the oxygen sensor are different, which indicates that the monitoring method of the patent can detect oil stains on different types of oil absorption materials.
Example 7:
example 7 the same method as in example 3, except that the signal acquisition device is not positioned in the body of waterAt the same time, the distance from the water surface is 1cm, 2cm, 3cm, 4cm and 5cm respectively, the oil absorption material is a circular composite oil absorption cotton piece, and the area is about 100cm2: the voltage signal value is monitored on line by the optical fiber oxygen sensor and is drawn into a curve, as shown in fig. 5, the result shows that the positions of the signal acquisition devices in the water body are different, the obtained voltage signal value of the oxygen sensor changes slightly, and the change of the positions of the detection points has almost no influence on the response of the oxygen signal value.
Example 8:
the apparatus of example 1 was replaced with an oxygen-consuming oxygen sensor (Shanghai Hengheng electromechanical instruments, Inc., JPB-607) and the apparatus of example 1 was otherwise the same.
Adding 35g of sodium chloride (NaCl) into 1000mL of water at 25 ℃, and stirring by a glass rod to uniformly dissolve the sodium chloride (NaCl) to obtain simulated seawater; fixing a probe of an oxygen consumption type oxygen sensor (Shanghai Hengheng electromechanical instrument, Inc., JPB-607) in a hydrophobic composite oil absorption cotton sheet, and monitoring the voltage signal value of the simulated seawater on line through the oxygen sensor; and then adding 20mL of engine oil into the simulated seawater to simulate an oil leakage event and an oil overflow event, and slightly shaking the engine oil to obtain a voltage signal value of the oxygen-consuming type oxygen sensor and drawing a change curve, as shown in FIG. 6, it is found that the change of the voltage signal value of the oxygen-consuming type oxygen sensor is different from that of the embodiment 3, that is, in the monitoring process of oil overflow and oil contamination, the change of the voltage signal value of the oxygen-consuming type oxygen sensor is different from that of the oxygen-consuming type oxygen sensor and the oxygen-consuming type oxygen sensor, and the change of the voltage signal value obtained by applying the oxygen-consuming type oxygen sensor is more obvious.
Claims (9)
1. An oil stain on-line monitoring method based on a hydrophobic oil absorption material is characterized in that: the online oil stain monitoring method adopts an online oil stain monitoring device to perform online monitoring, and the online oil stain monitoring device comprises a signal acquisition device, a signal transmission device and a signal processing device; the signal acquisition device transmits signals to the signal processing device through the signal transmission device; the signal acquisition and measurement device consists of 1 or more oxygen sensors and a hydrophobic oil absorption material, wherein the probe part of the oxygen sensor is fixed in the hydrophobic oil absorption material;
the oil stain online monitoring method comprises the following steps:
(1) under the set temperature, the signal acquisition device is arranged in the water body without oil pollution, the initial oxygen content in the hydrophobic oil absorption material under the condition of no oil pollution is obtained through the oxygen sensor, and the corresponding voltage signal value V at the moment is recorded0；
Adding oil stains into a water body without oil stains, monitoring the change of oxygen content in the hydrophobic oil absorption material on line, drawing a curve of voltage signal values changing along with time, enabling the voltage signal values changing along with time to be stable, and recording the stable voltage signal values; changing the amount of the added oil stain, drawing a curve of the voltage signal value changing along with time, and recording a stable voltage signal value, wherein when the stable voltage signal value is observed not to increase along with the increase of the oil stain amount any more, the oil stain adsorption amount of the monitoring device is saturated at the moment; storing the voltage signal value time-varying curves of the oil stain under different dosage conditions, wherein the curves have the same voltage signal value rising slope at the initial adsorption stage;
changing the category of the oil stains, and obtaining a voltage signal value time-varying curve of different oil stains under different using amounts according to the method; different oil stains have different voltage signal value rising slopes at the initial adsorption stage;
(2) changing the temperature, and obtaining voltage signal value time-varying curves of different oil stains under different consumption conditions at different temperatures according to the method in the step (1);
(3) measuring the temperature of the water body to be measured, placing the same signal acquisition device in the water body to be measured, monitoring the change of the oxygen content in the hydrophobic oil absorption material on line, drawing a curve of the change of the voltage signal value along with the time, and after the voltage signal value is stable, obtaining the voltage signal value and V0The oil pollution condition of the water body to be detected is obtained through the numerical value change, if the voltage signal value is increased, the oil pollution is shown, the oil pollution category is determined according to the rising slope of the voltage signal value of the adsorption initial stage at the temperature, and then the time change curve of the voltage signal value of the water body to be detected and the voltage of the determined oil pollution under the condition of no use amount at the temperature are combinedMatching the signal value with a time change curve to determine the oil stain content;
the oxygen sensor is a non-oxygen-consuming optical fiber oxygen sensor based on a fluorescence quenching principle or an electrochemical oxygen-consuming oxygen sensor.
2. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 1, characterized in that: the optical fiber oxygen sensor is detachably connected with the probe part by the sensor main body part; the sensor main body part consists of a hollow shell, a blue light source, a red light source, a light source driver, a conducting optical fiber, a fluorescence receiving plate, a red light filter, a photoelectric sensing device, a signal acquisition card, a signal identifier and a control circuit board, wherein the blue light source and the red light source are integrated in the shell; the probe part consists of a cover body matched with the shell and an oxygen sensitive layer which is integrated in the cover body and can excite fluorescence; the cover body is provided with a through hole, and an optical isolation layer which can permeate oxygen is arranged at the through hole; the optical isolation layer in the cover body is sequentially provided with an oxygen sensitive layer and a transparent carrier sheet from bottom to top;
the LED light source is in driving connection with the light source;
the end of the shell close to the cover body is provided with an opening, the direction of the opening is the same as the emitting direction of the LED light source, and a channel for emitting light or reflecting light of the LED light source is formed and used for guiding the emitting light to the oxygen sensitive layer;
the fluorescence receiving plate guides the fluorescence emitted by the oxygen sensitive layer to the photoelectric sensing device, a red light filter is arranged at the light inlet end of the photoelectric sensing device, and the photoelectric sensing device is connected with the receiving end of the conducting optical fiber;
the signal acquisition card is connected with the conductive rear end of the conductive optical fiber and is stored in the signal identifier;
the light source driving and photoelectric sensing device and the signal identifier are respectively electrically connected with the control circuit board;
the whole optical fiber oxygen sensor is of a closed structure.
3. The method for on-line monitoring oil stain based on the hydrophobic oil absorption material as claimed in claim 1 or 2, wherein the method comprises the following steps: 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.
4. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 2, characterized in that: the light source is blue light with the wavelength of 475nm and red light with the wavelength of 600 nm.
5. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 2, characterized in that: the sensor body part and the probe part can be connected through threads or buckles.
6. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 2, characterized in that: the optical isolation layer is silicone.
7. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 2, characterized in that: the oxygen sensitive layer is an oxygen sensitive fluorescent film containing an oxygen sensitive fluorescent indicator tri (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride.
8. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 2, characterized in that: the control circuit board is a single chip with model MSP43f149, and comprises: the control unit module is connected with the transmitting unit module and the data processing module and is used for controlling the transmitting unit module and the data processing module; the input end of the transmitting unit module is connected with the control unit module, and the output end of the transmitting unit module is connected with the light source for driving; the data processing module receives the electric signal which is transmitted by the photoelectric sensor and reflects the fluorescence intensity and directly sends out the electric signal, or the electric signal which reflects the fluorescence intensity is converted into wireless data through a signal converter and then is sent out.
9. The oil stain online monitoring method based on the hydrophobic oil absorption material as claimed in claim 1, characterized in that: the signal transmission device is an optical fiber cable, a USB data line, a wireless transceiver, a microwave transmitter or a satellite;
the signal processing device is a server computer, a microwave receiver or a data processor.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2436141A (en) * | 2006-03-17 | 2007-09-19 | Spectronic Devices Ltd | Sensor device |
| CN202159020U (en) * | 2011-07-25 | 2012-03-07 | 中国科学院烟台海岸带研究所 | Online fluorescence dissolved oxygen measuring device |
| CN102866136A (en) * | 2012-08-09 | 2013-01-09 | 中国科学院烟台海岸带研究所 | Probe type on-line monitoring system and probe type on-line monitoring method for water petroleum pollutants |
| CN106442423A (en) * | 2016-11-30 | 2017-02-22 | 吉林大学 | Contact type oil spill monitoring system based on SPR sensing principle |
| CN107449762A (en) * | 2017-08-15 | 2017-12-08 | 重庆三峡学院 | A kind of coil type monitoring method and equipment for spilled oil on water surface pollution prewarning |
| CN108548644A (en) * | 2018-03-29 | 2018-09-18 | 中国科学院合肥物质科学研究院 | A kind of unicom petroleum storage tank leakage monitor based on optical fiber oxygen sensor |
| CN108799845A (en) * | 2018-07-12 | 2018-11-13 | 北京目黑科技有限公司 | A kind of leakage detection device and its Oil Leakage Detecting cable and detection method |
-
2019
- 2019-06-28 CN CN201910575591.8A patent/CN110231374B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2436141A (en) * | 2006-03-17 | 2007-09-19 | Spectronic Devices Ltd | Sensor device |
| CN202159020U (en) * | 2011-07-25 | 2012-03-07 | 中国科学院烟台海岸带研究所 | Online fluorescence dissolved oxygen measuring device |
| CN102866136A (en) * | 2012-08-09 | 2013-01-09 | 中国科学院烟台海岸带研究所 | Probe type on-line monitoring system and probe type on-line monitoring method for water petroleum pollutants |
| CN106442423A (en) * | 2016-11-30 | 2017-02-22 | 吉林大学 | Contact type oil spill monitoring system based on SPR sensing principle |
| CN107449762A (en) * | 2017-08-15 | 2017-12-08 | 重庆三峡学院 | A kind of coil type monitoring method and equipment for spilled oil on water surface pollution prewarning |
| CN108548644A (en) * | 2018-03-29 | 2018-09-18 | 中国科学院合肥物质科学研究院 | A kind of unicom petroleum storage tank leakage monitor based on optical fiber oxygen sensor |
| CN108799845A (en) * | 2018-07-12 | 2018-11-13 | 北京目黑科技有限公司 | A kind of leakage detection device and its Oil Leakage Detecting cable and detection method |
Non-Patent Citations (1)
| Title |
|---|
| 一种准分布式光纤光栅漏油传感器;姜德生 等;《光学与光电技术》;20040229;第2卷(第1期);第15-19、33页 * |
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