A seawater oil spill classification detection device

Abstract

The invention discloses a seawater oil spill classification detection device, which belongs to the field of multi-spectral measurement technology, and includes an automatic circulation platform, an optical detection system and an automatic control unit; the automatic circulation platform collects seawater containing oil spills, and sends the seawater sample and the constant temperature mixed liquid of seawater and nanomaterials into the cuvette in a time-sharing manner; the optical detection system uses a laser light source that can excite a fluorescent signal to irradiate the seawater sample in the cuvette to excite the fluorescent signal and collect it to generate fluorescent spectrum data; or uses a laser light source that can excite a Raman light signal to irradiate the constant temperature mixed liquid in the cuvette to excite the Raman light signal and collect it to generate Raman spectrum data; the automatic control unit receives the fluorescent spectrum data and the Raman spectrum data, and executes the seawater oil spill classification detection process. The device of the invention can improve the speed and accuracy of oil spill classification detection, and can realize in-situ detection of seawater, solving the problem of difficulty in tracing the source of oil spills.

Description

[0001] This application is a divisional application with an application date of May 23, 2022, application number 202210559319.2, and invention name “Device and method for classifying and detecting seawater oil spills using spectral analysis technology”. Technical Field

[0002] The invention belongs to the technical field of multi-spectral measurement, and in particular relates to a device for classifying and detecting seawater oil spills by using spectral analysis technology. Background Art

[0003] With the rise of offshore oil exploration and exploitation, offshore oil spills and oil spills from oil tankers have occurred frequently, causing a large amount of oil and various types of oil products to flow into the ocean, causing serious pollution to the marine environment. Since the supervision of crude oil and refined oil production often belongs to different law enforcement departments, when oil pollutants appear in seawater, it is first necessary to determine the type of oil spill, and then determine the relevant law enforcement department for supervision and management and traceability based on the type of oil spill. Therefore, it is necessary for some law enforcement departments to classify and detect seawater oil spills. At the same time, rapid and accurate classification of seawater oil spills is also conducive to the efficient implementation of offshore oil pollution removal work.

[0004] At present, the most common methods for detecting and classifying petroleum and its various oil products are liquid chromatography and gas chromatography. These methods require sampling of oil spills in seawater and sending them to laboratories, where large equipment is used to complete the classification and detection of oil products. This is not only time-consuming and costly, but also has poor timeliness, making it difficult to trace back later. Summary of the invention

[0005] The purpose of the present invention is to provide a device for classifying and detecting oil spills in seawater by using spectral analysis technology, and to improve the efficiency and accuracy of classifying and detecting oil spills in seawater by combining fluorescence spectrum and Raman spectrum.

[0006] In order to achieve the above technical objectives, the present invention adopts the following technical solutions:

[0007] A seawater oil spill classification detection device includes an automatic circulation platform, an optical detection system and an automatic control unit; wherein:

[0008] The automatic circulation platform is used to collect seawater containing oil spills, and to mix the seawater with nanomaterials required for surface enhanced Raman spectroscopy detection at a constant temperature, and to feed the seawater sample and the constant temperature mixed liquid into the cuvette in a time-sharing manner to perform fluorescence spectroscopy detection and Raman spectroscopy detection respectively;

[0009] The optical detection system utilizes a laser light source capable of exciting a fluorescence signal to illuminate a seawater sample in a cuvette to stimulate and collect the fluorescence signal, thereby generating fluorescence spectrum data; or utilizes a laser light source capable of exciting a Raman light signal to illuminate a constant temperature mixed liquid in a cuvette to stimulate and collect the Raman light signal, thereby generating Raman spectrum data; it comprises:

[0010] A fluorescence optical path system, comprising a fluorescent laser light source, a first collimating lens, a first narrowband filter, a first converging lens, a second collimating lens, a first long-wave pass filter, a second converging lens and a fluorescence detector; wherein the fluorescent laser light source is used to emit a 360nm laser, which is processed into parallel light by the first collimating lens, emitted to the first narrowband filter to eliminate stray light other than 360nm, and then converged to the cuvette through the first converging lens to irradiate the seawater containing oil spill in the cuvette to stimulate a fluorescent signal; the second collimating lens collects the fluorescent signal, and emits it to the long-wave pass filter as parallel light to filter out interference light of non-fluorescent signals, and then converges to the fluorescent detector through the second converging lens to realize the collection of fluorescent spectrum data;

[0011] A Raman optical path system comprises a differential Raman laser, a third collimating lens, a short-wave pass dichroic mirror, a second narrow-band filter, a third narrow-band filter, a first long-wave pass dichroic mirror, a third converging lens, a second long-wave pass dichroic mirror, a second long-wave pass filter, a fourth converging lens and a Raman detector; wherein the differential Raman laser is used to emit 785nm and 830nm lasers, which are processed into parallel light by the third collimating lens and then emitted to the short-wave pass dichroic mirror, and the short-wave pass dichroic mirror is transparent to the 785nm laser and reflects the 830nm laser, so as to form two laser beams for split transmission; wherein the 785nm laser is emitted to the first long-wave pass dichroic mirror after the stray light other than 785nm is filtered out by the second narrow-band filter; the 830nm laser is emitted to the first long-wave pass dichroic mirror by the second narrow-band filter; the 830nm laser is emitted to the first long-wave pass dichroic mirror by the third collimating lens. After the third narrow-band filter filters out stray light other than 830nm, it is reflected to the first long-wave-pass dichroic mirror through the second long-wave-pass dichroic mirror; the first long-wave-pass dichroic mirror reflects the 785nm laser and transmits the 830nm laser, so that the two laser beams of 785nm and 830nm are converged to the cuvette through the third converging lens to irradiate the constant-temperature mixed liquid in the cuvette to excite two Raman light signals of 785nm and 830nm; the two Raman light signals are respectively transmitted to the second long-wave-pass filter through the third converging lens, the first long-wave-pass dichroic mirror and the second long-wave-pass dichroic mirror to filter out non-Raman light signals less than 830nm, and are converged to the Raman detector through the fourth converging lens to realize the collection of Raman spectrum data;

[0012] The automatic control unit is used to receive the fluorescence spectrum data and the Raman spectrum data, and perform the following seawater oil spill classification detection process:

[0013] Perform spectral smoothing and noise removal on the fluorescence spectrum data to obtain a smoothed fluorescence spectrum graph;

[0014] Performing baseline correction on the smoothed fluorescence spectrum to remove the local baseline;

[0015] Peak picking is performed on the fluorescence spectrum after the local baseline is removed, and the spectral positions and intensities of all characteristic peaks are picked out;

[0016] The spectral position and intensity of the picked characteristic peak are compared with the fluorescence spectrum of gasoline and diesel to identify whether the spilled oil is gasoline or diesel;

[0017] When the spilled oil is not gasoline or diesel, performing spectral smoothing and noise removal processing on the Raman spectrum data to obtain a smoothed Raman spectrum graph;

[0018] Performing baseline correction on the smoothed Raman spectrum to remove the local baseline;

[0019] Peak picking is performed on the Raman spectrum after the local baseline is removed, and the spectral positions and intensities of all characteristic peaks are picked out;

[0020] The spectral position and intensity of the picked-up characteristic peaks are compared with the Raman spectra of the PAH types of crude oil and refined oil to identify the PAH types contained in the spilled oil;

[0021] The type of oil spill can be identified based on the types of PAHs contained in the oil and the proportion of each type of PAHs.

[0022] In some embodiments of the present application, the automatic circulation platform includes:

[0023] A first three-way valve, wherein a first selection port is used for injecting the nanomaterial, and a second selection port is used for receiving a pipeline cleaning liquid;

[0024] a second three-way valve, wherein a first selection port thereof is connected to a common port of the first three-way valve;

[0025] a constant temperature mixing circulation pipe, the water inlet of which is connected to the common port of the second three-way valve;

[0026] A third three-way valve, wherein the first selection port is used for sampling seawater containing spilled oil, and the second selection port is connected to the outlet of the constant temperature mixing circulation pipe;

[0027] a peristaltic pump, whose water inlet is connected to the common port of the third three-way valve;

[0028] a fourth three-way valve, wherein the common port thereof is connected to the water outlet of the peristaltic pump, the first selection port thereof is connected to the second selection port of the second three-way valve, and the second selection port of the fourth three-way valve is connected to the cuvette;

[0029] Wherein, in the process of classifying and detecting the oil spill in seawater, the automatic control unit performs the following control process on the automatic circulation platform:

[0030] Control the common port of the third three-way valve to be connected to the first selection port thereof, control the common port of the fourth three-way valve to be connected to the second selection port thereof, start the peristaltic pump, and pump the seawater containing the spilled oil into the cuvette for fluorescence spectrum detection;

[0031] Control the common ports of the first three-way valve, the second three-way valve and the fourth three-way valve to be connected to the first selection port thereof, control the common port of the third three-way valve to be connected to the second selection port thereof, and pump the nanomaterial into the constant temperature mixing circulation pipe;

[0032] Control the common port of the second three-way valve to be connected with the second selection port thereof, control the common port of the third three-way valve to be connected with the first selection port thereof, and pump in a certain amount of seawater containing spilled oil;

[0033] Control the common port of the third three-way valve to communicate with the second selection port of the third three-way valve to form a mixing loop, so that the seawater and the nanomaterial are fully mixed through the constant temperature mixing circulation pipe and kept at a constant temperature to form a constant temperature mixed liquid;

[0034] Controlling the common port of the fourth three-way valve to communicate with the second selection port thereof, and pumping the constant temperature mixed liquid into the cuvette for Raman spectrum detection;

[0035] After the Raman spectrum detection is completed, the common port of the first three-way valve is controlled to be connected to the second selection port thereof, and the common ports of the second three-way valve and the fourth three-way valve are controlled to be connected to the first selection port thereof, so as to pump the pipeline cleaning fluid into the pipeline of the automatic circulation platform;

[0036] Control the common port of the second three-way valve to be connected with the second selection port of the second three-way valve to form a cleaning loop to clean the pipeline of the automatic circulation platform;

[0037] The common port of the fourth three-way valve is controlled to be connected with the second selection port thereof to clean the cuvette.

[0038] Compared with the prior art, the advantages and positive effects of the present invention are mainly reflected in:

[0039] The seawater oil spill classification detection device of the present invention adopts fluorescence spectroscopy to identify gasoline and diesel, adopts Raman spectroscopy to identify crude oil, fuel oil and light oil, and adopts differential Raman to eliminate fluorescence interference in Raman spectrum. By smoothing and denoising, baseline correction and peak picking of fluorescence spectrum and Raman spectrum, accurate picking of characteristic peak position and intensity is achieved, and the problem of easy error in oil product identification caused by inaccurate estimation of characteristic peak position is solved, thereby improving the accuracy of seawater oil spill classification detection.

[0040] The seawater oil spill classification detection device of the present invention combines fluorescence spectrum detection and Raman spectrum detection on the basis of an automatic circulation platform, and adopts an automatic control strategy to achieve complete mixing and constant temperature control of the nanomaterials and seawater oil spills required for Raman spectrum detection, and realizes the automatic cleaning function of the circulation pipeline, thereby automatically completing the entire process from seawater sampling, mixing, oil spill excitation, light signal collection, spectrum processing to oil spill classification and identification, which not only improves the speed and accuracy of oil spill classification detection, but also can realize in-situ detection of seawater, solving the problem of difficulty in tracing the source of oil spills.

[0041] Other features and advantages of the present invention will become more apparent after reading the detailed description of the embodiments of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 It is an overall architecture diagram of an embodiment of the automatic circulation platform in the seawater oil spill classification detection device proposed by the present invention;

[0044] Figure 2 It is an overall architecture diagram of an embodiment of the optical detection system in the seawater oil spill classification detection device proposed by the present invention;

[0045] Figure 3 It is a processing flow chart of an embodiment of a method for detecting seawater oil spill classification;

[0046] Figure 4 It is a smoothed fluorescence spectrum obtained after smoothing and denoising the original fluorescence spectrum data;

[0047] Figure 5 Yes Figure 4 The spectrum obtained after baseline correction of the smoothed fluorescence spectrum shown;

[0048] In the figure, 10, cuvette; 11, first three-way valve; 12, second three-way valve; 13, third three-way valve; 14, fourth three-way valve; 15, constant temperature mixing circulation tube; 16, peristaltic pump; 21, fluorescent laser light source; 22, first collimating lens; 23, first narrow-band filter; 24, first converging lens; 25, second collimating lens; 26, first long-wave pass filter; 27, second converging lens; 28, fluorescence detector; 31, differential Raman laser; 32, third collimating lens; 33, short-wave pass dichroic mirror; 34, second narrow-band filter; 35, reflecting mirror; 38, third narrow-band filter; 36, first long-wave pass dichroic mirror; 37, third converging lens; 39, second long-wave pass dichroic mirror; 40, second long-wave pass filter; 41, fourth converging lens; 42, Raman detector. DETAILED DESCRIPTION

[0049] The specific implementation modes of the present invention are described in detail below with reference to the accompanying drawings.

[0050] It should be noted that in the description of the present invention, the terms "front", "rear" and other terms indicating directions or positional relationships are based on the directions or positional relationships shown in the drawings, which are only for the convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore, cannot be understood as limiting the present invention. In addition, the terms "first", "second", "third" and "fourth" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0051] In addition, it should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "connected" and "connection" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a direct connection, or an indirect connection through an intermediate medium, or it can be the internal communication of two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to the specific circumstances.

[0052] An important feature of marine oil spills is that they occur suddenly, and a small amount of oil spills cannot be discovered quickly and accurately, making it difficult to trace them later. Based on this, this embodiment designs an automatic circulation analysis platform, and combines spectroscopy to achieve unattended, rapid analysis and determination of the oil spill site, providing a basis for rapid tracing and accurate classification of marine oil spill accidents.

[0053] Spectral analysis technology can measure oil in seawater, but a single spectral analysis technology cannot achieve high sensitivity and accurate classification and determination. An important feature of seawater oil spills is that the oil contains a variety of polycyclic aromatic hydrocarbons, which have fluorescence and Raman characteristics. For gasoline and diesel, the fluorescence characteristic peaks of the polycyclic aromatic hydrocarbons they contain are clearly distinguished, and the position of the characteristic peaks of the fluorescence spectrum can be used to identify whether the oil spill is gasoline or diesel. For crude oil, fuel oil, light oil, etc., since the fluorescence characteristic peaks of some polycyclic aromatic hydrocarbons they contain overlap, it is impossible to accurately distinguish the types of such oil spills using only fluorescence spectroscopy. However, the Raman characteristic peaks of the polycyclic aromatic hydrocarbons in this type of oil spill are different. Therefore, the quantitative and qualitative analysis of different polycyclic aromatic hydrocarbons can be achieved by measuring the peak position and intensity of the Raman characteristic peaks, thereby identifying the type of such oil spill.

[0054] Based on this, this embodiment combines fluorescence spectroscopy technology and Raman spectroscopy technology on an automatic circulation analysis platform for the classification and detection of oil spill pollutants, which can not only save manpower and improve the efficiency and accuracy of oil spill classification and detection, but also make up for the shortcomings of laboratory methods and single spectral analysis methods, becoming a new method for rapid detection of organic pollutants in the environment.

[0055] Since fluorescence interference is usually present when measuring Raman spectrum, which affects the accuracy of the Raman measurement result, this embodiment uses differential Raman spectroscopy technology to remove fluorescence interference to achieve accurate measurement of Raman spectrum.

[0056] Based on the above design concept, this embodiment first designs a set of seawater oil spill classification detection equipment to support in-situ detection of seawater oil spills, which specifically includes main components such as an automatic circulation platform, an optical detection system and an automatic control unit.

[0057] The functions to be completed by the automatic circulation platform of this embodiment mainly include:

[0058] (1) Collecting seawater containing oil spills can be done on-site or in the laboratory;

[0059] (2) The collected seawater is sent into a cuvette for fluorescence spectrum detection;

[0060] (3) The collected seawater is mixed with the nanomaterials (e.g., a solution of gold nanoparticles) required for Raman spectroscopy detection at a constant temperature, and then the constant temperature mixed liquid is sent into a cuvette for Raman spectroscopy detection;

[0061] (4) Automatically clean the circulation pipeline and cuvette.

[0062] To achieve the above functions, Figure 1As shown, in this embodiment, the automatic circulation platform is mainly configured with four three-way valves 11-14 (defined as the first three-way valve 11, the second three-way valve 12, the third three-way valve 13, and the fourth three-way valve 14, respectively), a constant temperature mixing circulation tube 15 and a peristaltic pump 16.

[0063] The first selection port NC1 of the first three-way valve 11 is used for injecting nanomaterials required for Raman spectroscopy detection, the second selection port NO1 is used for connecting pipeline cleaning liquid, and the common port COM1 is connected to the first selection port NC2 of the second three-way valve 12 .

[0064] The second selection port NO2 of the second three-way valve 12 is connected to the first selection port NC4 of the fourth three-way valve 14 , and the common port COM2 of the second three-way valve 12 is connected to the water inlet of the constant temperature mixing circulation pipe 15 .

[0065] The first selection port NC3 of the third three-way valve 13 is used to sample seawater containing spilled oil, the second selection port NO3 is connected to the water outlet of the constant temperature mixing circulation pipe 15, and the common port COM3 of the third three-way valve 13 is connected to the water inlet of the peristaltic pump 16.

[0066] The common port COM4 of the fourth three-way valve 14 is connected to the water outlet of the peristaltic pump 16, and the second selection port NO4 of the fourth three-way valve 14 is connected to the cuvette 10. Figure 2 shown.

[0067] In this embodiment, the cuvette 10 is preferably a corrosion-resistant quartz cuvette, the lower end of which is a sample inlet connected to the second selection port NO4 of the fourth three-way valve 14, and the upper end is a sample outlet, which can effectively avoid gas interference.

[0068] As a preferred embodiment, the normally closed ports of the four three-way valves 11-14 can be used as the first selection port, and the normally open ports can be used as the second selection port to simplify the control process and avoid frequent switching control of the valve body.

[0069] The functions to be completed by the optical detection system of this embodiment mainly include:

[0070] (1) Using a laser light source that can excite fluorescence signals to illuminate the seawater sample in the cuvette to excite and collect fluorescence signals to generate fluorescence spectrum data;

[0071] (2) A laser light source capable of stimulating Raman light signals is used to illuminate the constant temperature mixed liquid in the cuvette to stimulate and collect Raman light signals to generate Raman spectral data.

[0072] To achieve the above functions, Figure 2As shown, in the optical detection system of this embodiment, a fluorescence optical path system and a Raman optical path system are mainly configured. Among them, the fluorescence optical path system mainly includes a fluorescent laser light source 21, a first collimating lens 22, a first narrowband filter 23, a first converging lens 24, a second collimating lens 25, a first long-wave pass filter 26, a second converging lens 27 and a fluorescence detector 28. The Raman optical path system mainly includes a differential Raman laser 31, a third collimating lens 32, a short-wave pass dichroic mirror 33, a second narrowband filter 34, a reflector 35, a third narrowband filter 38, a first long-wave pass dichroic mirror 36, a third converging lens 37, a second long-wave pass dichroic mirror 39, a second long-wave pass filter 40, a fourth converging lens 41 and a Raman detector 42.

[0073] Among them, the fluorescent laser light source 21 preferably adopts an ultra-high brightness LED light source, with a spectral range between 355nm and 365nm, a divergence angle of 60°, and an optical power of 0.5W. This embodiment is described by taking a 360nm laser as an example. The ultra-high brightness 360nm laser with a power of up to 0.5W can effectively excite the detection object to emit a fluorescent signal, and the divergence angle of 60° can meet the requirements of the subsequent lens for light collimation processing.

[0074] The first collimating lens 22 is located behind the fluorescent laser light source 21 (the front and the rear are defined by the transmission direction of the light), and is used to collimate the 360nm laser emitted by the fluorescent laser light source 21 to achieve parallel emission of the light beam and ensure parallel transmission of the light in the optical fiber.

[0075] The first narrow-band filter 23 is located behind the first collimating lens 22 and is used to eliminate stray light with a wavelength other than 360 nm and the monochromaticity of the excitation light, thereby effectively avoiding the problems of complex and difficult-to-distinguish fluorescence signals caused by wide-spectrum excitation.

[0076] The first converging lens 24 is located behind the first narrow-band filter 23 and is used to converge the 360nm laser into the quartz cuvette 10, and use the small spot, high-energy 360nm laser to excite the seawater containing the oil spill to ensure that the oil spill emits a fluorescent signal.

[0077] The second collimating lens 25 is used to collect the excited fluorescent signal. Since the excited fluorescent signal is scattered light without a specific direction, a lens with a specific focal length and diameter is required to collect the fluorescent signal so that the fluorescent signal passes through the first long-wave filter 26 as parallel light as possible to filter out stray light.

[0078] The first long-wave filter 26 is located behind the second collimating lens 25 and is used to filter out stray light other than the fluorescence signal. The fluorescence signal is often accompanied by 360nm reflected light and other interfering light. The use of a long-wave filter can filter out the interference of other light on fluorescence detection.

[0079] The second converging lens 27 is located behind the first long-wave pass filter 26 and is used to converge the fluorescence signal on the fluorescence detector 28, so as to achieve effective detection of fluorescence through the fluorescence detector 28.

[0080] In this embodiment, the fluorescence detector 28 can be a spectrometer for fluorescence signal detection, with a spectral range between 200nm and 600nm, and is mainly used for receiving and photoelectric conversion of fluorescence signals to achieve output of fluorescence spectrum data.

[0081] The differential Raman laser 31 preferably adopts a 785nm / 830nm differential Raman laser, that is, it can emit lasers of two wavelengths, 785nm and 830nm, with a maximum line width of 0.1nm, a maximum output power of 600mW, an output fiber optic interface FC / PC, and an external optical fiber to ensure the light output efficiency and facilitate the rear lens to collimate the light.

[0082] The third collimating lens 32 is located behind the differential Raman laser 31 and is used for collimating the laser to achieve parallel emission of the light beam.

[0083] The short-wave dichroic mirror 33 is located behind the third collimating lens 32 and is placed at a 45° angle to transmit the 785nm laser and reflect the 830nm laser, thereby realizing the split transmission of the two laser beams.

[0084] The second narrowband filter 34 is located behind the short-wave pass dichroic mirror 33 and is used to transmit the 785nm laser and filter out stray light other than the 785nm laser to achieve the monochromaticity of the light beam to meet the requirements of Raman signal excitation.

[0085] The reflector 35 is located behind the second narrowband filter 34 and is placed at an angle of 45° to reflect the 785nm laser to redirect the light path, shorten the light path length, and realize backward detection.

[0086] The first long-wave dichroic mirror 36 is located below the reflector 35 and is placed at a 45° angle to reflect the 785nm laser and transmit Raman light greater than 785nm to achieve the steering of the 785nm laser beam and filter out stray light in the collected Raman signal.

[0087] The third converging lens 37 is located between the first long-wave dichroic mirror 36 and the quartz cuvette 10, and is used to converge the 785nm and 830nm lasers to form a small spot, so as to increase the energy per unit area of ​​the light beam, so that the two laser beams can excite the constant temperature mixed liquid in the cuvette to emit Raman scattered light. At the same time, it is also used to collect the Raman scattered light generated by the two laser beams, so that the Raman scattered light can pass through the subsequent optical devices as parallel light as possible to achieve stray light filtering.

[0088] The third narrowband filter 38 is used to transmit the 830nm laser reflected by the short-wave pass dichroic mirror 33 and filter out stray light other than 830nm to achieve the monochromaticity of the light beam to meet the requirements of Raman light signal excitation.

[0089] The second long-wave dichroic mirror 39 is placed at an angle of 45°, and reflects the 830nm laser to the first long-wave dichroic mirror 36, and is transmitted to the third converging lens 37 through the first long-wave dichroic mirror 36 to form a small spot, high-energy 830nm laser to irradiate the constant temperature mixed liquid in the cuvette 10 to excite the Raman scattered light belonging to 830nm.

[0090] The third converging lens 37 collects the two Raman scattered lights of 785nm and 830nm, processes them into parallel lights, and sequentially transmits them through the first long-wave pass dichroic mirror 36 and the second long-wave pass dichroic mirror 39. The first long-wave pass dichroic mirror 36 and the second long-wave pass dichroic mirror 39 have the characteristic of transmitting Raman light, and transmit the two Raman lights to the second long-wave pass filter 40.

[0091] The second long-wave pass filter 40 is used to filter out non-Raman light, mainly to eliminate the influence of 785nm and 830nm reflected light on Raman detection.

[0092] The fourth converging lens 41 is located behind the second long wave pass filter 40 and is used to converge the Raman light onto the Raman detector 42 so as to achieve effective detection of the Raman light through the Raman detector 42.

[0093] In this embodiment, the Raman detector 42 can be selected as a spectrometer for Raman signal detection, and the Raman frequency shift range is 150cm -1 ~3500cm -1 , mainly used for receiving and photoelectric conversion of Raman signals to realize the output of Raman spectrum data.

[0094] As a preferred embodiment, surface enhanced Raman spectroscopy (SERS) is preferably used for Raman detection. When surface enhanced Raman spectroscopy is used to detect oil spill pollutants, fluorescence is often generated. The fluorescence signal is stronger than the Raman signal, which will cause the Raman signal to be submerged in the fluorescence and make it impossible to extract useful Raman signals. When the oil spill pollutants are excited to produce Raman spectra by lasers with wavelengths of 785nm and 830nm, the fluorescence signal will not be significantly displaced, while the spectral characteristic peaks of the Raman spectrum will shift with the excitation light and maintain a certain positional relationship with the excitation light. Therefore, by subtracting the Raman characteristic spectrum of the oil spill excited by the laser with a wavelength of 785nm from the Raman characteristic spectrum of the oil spill excited by the laser with a wavelength of 830nm, the Raman spectrum information with fluorescence eliminated can be obtained, thereby improving the accuracy of Raman detection.

[0095] The automatic control unit is mainly used to control the path switching of the four three-way valves 11-14 in the automatic circulation platform and the switching control of the constant temperature mixing circulation tube 15 and the peristaltic pump 16; at the same time, it controls the switching timing of the fluorescent laser light source 21 and the differential Raman laser 31 in the optical detection system, and receives the fluorescence spectrum data and Raman spectrum data output by the fluorescence detector 28 and the Raman detector 42 to perform classification detection of seawater oil spills.

[0096] Combine the following Figure 1 and Figure 2 The seawater oil spill classification detection device shown is used to describe in detail the seawater oil spill classification detection method proposed in this embodiment.

[0097] First, the collected seawater containing oil spills is subjected to fluorescence detection, which specifically includes the following processes:

[0098] The automatic control unit first controls the common port COM3 of the third three-way valve 13 in the automatic circulation platform to be connected with its first selection port NC3, and controls the common port COM4 of the fourth three-way valve 14 to be connected with its own second selection port NO4, starts the peristaltic pump 16, and pumps seawater containing spilled oil into the cuvette 10 for about 10 seconds for fluorescence spectrum detection.

[0099] The automatic control unit starts the fluorescent laser light source 21 in the optical detection system to emit 380nm laser, and starts the fluorescent detector 28 to collect the fluorescent signal stimulated by the seawater oil spill to generate fluorescent spectrum data.

[0100] The automatic control unit collects the fluorescence spectrum data output by the fluorescence detector 28 and performs the following processing, combining Figure 3 As shown:

[0101] S301, performing spectrum smoothing and noise removal processing on the fluorescence spectrum data to obtain a smoothed fluorescence spectrum graph.

[0102] Since the collected fluorescence spectrum contains a lot of noise, if the fluorescence information is directly extracted, the noise will affect the extraction effect. In this embodiment, the fluorescence spectrum data can be smoothed and denoised using Savitzky-Golay polynomial smoothing, and spectral denoising can be achieved through weighted averaging.

[0103] The specific process is: convolution operation is performed on the collected spectral data P[n] and the smoothing weight vector W[n], and the formula is:

[0104]

[0105] Among them, n i is the i-th spectral data; z is the total number of spectral data, and m is an integer of z / 2; Wj is the smoothing weight factor; E[n] is the smoothed spectral data, and the effect after smoothing is as follows Figure 4 As shown ( Figure 4 In the figure, the horizontal axis represents the spectral position and the vertical axis represents the light intensity).

[0106] S302: Perform baseline correction on the smoothed fluorescence spectrum to remove the local baseline.

[0107] In this embodiment, a fluorescence dark background spectrum may be first obtained, and then the fluorescence dark background spectrum may be subtracted from a smoothed fluorescence spectrum to obtain a fluorescence spectrum after removing the local baseline, thereby completing baseline calibration.

[0108] The basic process of baseline calibration is:

[0109] First, find the baseline curve B[n] of the spectrum by comparing and analyzing each point in the original spectrum data P[n] with the spectrum data E[n] smoothed by Savitzky-Golay polynomial. i ] and E[n i ] for comparison, and take the smaller value of the two to generate the baseline curve B[n];

[0110] Secondly, the original spectral data P[n] is subtracted from the generated baseline data, and the trapezoidal method is used to integrate them to form a new matrix C[n];

[0111] Next, find the condition that C[n i-1 ]< C[n i-2 ]、C[n i-1 ]< C[n i ] i-1 , extract B[n i-1 ] Generate the minimum baseline B min [n];

[0112] Finally, the original spectral data P[n] and B min [n] is subtracted to obtain the spectrum data D[n] after baseline correction. The effect diagram after baseline correction is as follows Figure 5 As shown ( Figure 5 In the figure, the horizontal axis represents the spectral position and the vertical axis represents the light intensity).

[0113] S303, performing peak picking on the fluorescence spectrum after removing the local baseline, and picking out the spectral positions and intensities of all characteristic peaks.

[0114] In this embodiment, the spectral data after smoothing and baseline correction can be expressed as:

[0115] D[n]={n1, n2, n3,…,n z}.

[0116] To pick up the characteristic peaks in the fluorescence spectrum, the following characteristic peak picking process can be used:

[0117] Every five adjacent data points in the spectral data D[n] form a group of data, which can be recorded as A k {n i-2 , n i-1 , n i ,n i+1 , n i+2}, where n i represents the light intensity at the spectral coordinate i, i.e., the peak height;

[0118] Sort the 5 data points in each set of data in ascending order;

[0119] If three adjacent sets of data A k-1 , A k , A k+1 A k-1 The spectral coordinates are in ascending order, A k The spectral coordinates of A are out of order. k+1 The spectral coordinates of A are in descending order. k The position is determined as the characteristic peak position.

[0120] For example: Assume that A8, A9, A 10 After arranging the three sets of data in ascending order, we get:

[0121] A8{2643 742 ,2784 743 ,2832 744 ,2903 745 ,2923 746}

[0122] A9{3000 751 ,3115 748 ,3220 747 ,3314 750 ,3423 749}

[0123] A 10 {2822 752 ,2713 753 ,2590 754 ,2345 755 ,2212 756}.

[0124] Among them, the spectral coordinates of A8 are in ascending order, the spectral coordinates of A9 are in random order, 10The spectral coordinates are in descending order, therefore, A9 can be determined to be the position of a characteristic peak.

[0125] S304, compare the spectral position and intensity of the picked characteristic peak with the fluorescence spectrum of gasoline and diesel to identify whether the oil spill is gasoline or diesel. If it is gasoline or diesel, perform the oil spill concentration detection process, that is, jump to step S311; otherwise, use Raman detection technology to classify and identify the seawater oil spill.

[0126] Raman detection of the collected seawater containing oil spills includes the following processes:

[0127] First, the automatic control unit controls the common ports COM1, COM2, and COM4 of the first three-way valve 11, the second three-way valve 12, and the fourth three-way valve 14 in the automatic circulation platform to be connected with their own first selection ports NC1, NC2, and NC4 respectively, and controls the common port COM3 of the third three-way valve 13 to be connected with its own second selection port NO3, so as to pump the nanomaterials required for Raman spectroscopy detection into the constant temperature mixing circulation tube 15 to realize the sampling of the nanomaterials, and the time is about 10 seconds.

[0128] Then, the automatic control unit controls the common port COM2 of the second three-way valve 12 to be connected to its own second selection port NO2, and controls the common port COM3 of the third three-way valve 13 to be connected to its own first selection port NC3, pumping in a certain amount of seawater containing spilled oil to achieve the sampling of seawater samples. The pumping amount of seawater samples can be adjusted by controlling the sampling time of seawater samples to meet the requirements of Raman spectrum detection.

[0129] Then, the automatic control unit controls the common port COM3 of the third three-way valve 13 to communicate with its own second selection port NO3 to form a mixing loop, so that the seawater sample and the nanomaterial are fully mixed and kept at a constant temperature through the constant temperature mixing circulation pipe 15 to form a constant temperature mixed liquid. The mixing time is about 30 seconds.

[0130] Finally, the automatic control unit controls the common port COM4 of the fourth three-way valve 14 to be connected to its second selection port NO4, and pumps the constant temperature mixed liquid into the quartz cuvette 10 for about 10 seconds to perform Raman spectrum detection.

[0131] The automatic control unit starts the differential Raman laser 31 in the optical detection system to emit lasers with wavelengths of 785nm and 830nm, and starts the Raman detector 42 to collect two Raman optical signals excited by the seawater oil spill to generate two sets of Raman spectrum data.

[0132] The automatic control unit collects the Raman spectrum data output by the Raman detector 42 and performs the following processing, combining Figure 3 As shown:

[0133] S305 , performing a differential analysis on the collected Raman characteristic spectrum at 785 nm and the collected Raman characteristic spectrum at 830 nm to obtain Raman spectrum data after eliminating fluorescence, that is, differential surface enhanced Raman spectrum data.

[0134] S306 , performing spectral smoothing and noise removal processing on the differential surface enhanced Raman spectroscopy data to obtain a smooth SERS spectrum graph.

[0135] In this embodiment, the spectral smoothing and denoising process is performed on the differential surface enhanced Raman spectroscopy data. The same method as the spectral smoothing and denoising process for the fluorescence spectroscopy data can be used, that is, the Savitzky-Golay polynomial smoothing method is used to remove noise. The specific method can be seen in step S301.

[0136] S307, performing baseline correction on the smoothed SERS spectrum to remove the local baseline.

[0137] In this embodiment, the baseline correction of the smoothed SERS spectrum can be performed using the same method as the baseline correction of the smoothed fluorescence spectrum. For the specific process, see step S302.

[0138] S308, performing peak picking on the SERS spectrum after removing the local baseline, and picking out the spectral positions and intensities of all characteristic peaks.

[0139] In this embodiment, the peak picking is performed on the SERS spectrum after the local baseline is removed. The same method as the peak picking is performed on the fluorescence spectrum after the local baseline is removed. The specific process can be referred to step S303.

[0140] S309, comparing the spectral position and intensity of the picked-up characteristic peaks with the Raman spectra of the characteristics of the PAH types in crude oil and refined oil, and identifying the types of PAHs contained in the spilled oil.

[0141] S310. Identify the type of oil spill based on the types of PAHs contained in the oil spill and the proportion of each PAH content.

[0142] In this embodiment, the type of oil spill can be determined based on the proportion of five PAHs: naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene. The specific process is as follows:

[0143] Extract the peak heights of the characteristic peaks corresponding to the five substances of naphthalene, phenanthrene, anthracene, fluoranthene and pyrene in polycyclic aromatic hydrocarbons;

[0144] Calculating the sum of the peak heights of the five substances to form a total peak height;

[0145] Calculate the ratio of the sum of the peak heights of the characteristic peaks corresponding to the two substances naphthalene and phenanthrene to the total peak height;

[0146] If the proportion of naphthalene and phenanthrene is higher than 20%, it is judged as light oil;

[0147] If the proportion of naphthalene and phenanthrene is between 10% and 20%, it is judged to be fuel oil;

[0148] If the proportion of naphthalene and phenanthrene is less than 10%, it is judged to be crude oil.

[0149] S311. Detect the concentration of the spilled oil.

[0150] Since there is a linear relationship between the characteristic peaks in the spectrum and the sample concentration, the multiple linear regression analysis method can be used to achieve quantitative detection of oil spills.

[0151] The specific process is:

[0152] If the identified spilled oil is gasoline or diesel, all characteristic peak intensities in the fluorescence spectrum are extracted;

[0153] If the identified spilled oil is crude oil, fuel oil or light oil, all characteristic peak intensities in the Raman spectrum are extracted;

[0154] The following multiple linear regression model was used to calculate the oil spill concentration:

[0155] y=b0+b1x1+ b2x2+…+ b r x r +e;

[0156] Where y represents the oil spill concentration; x1, x2, …, x r represents the intensities of r characteristic peaks extracted from the fluorescence spectrum or Raman spectrum, where r is the total number of characteristic peaks; e is the random error term; b0 is the constant term; b1, b2, …, b r is the regression coefficient, where b1 is x2, x3, …, x r When x1 is fixed, the effect of each unit increase in x1 on y, that is, the partial regression coefficient of x1 on y; similarly, b2 is x1, x3, …, x r When x2 is fixed, the effect of each unit increase in x2 on y, that is, the partial regression coefficient of x2 on y; b r for x1, x2, …, x r-1 When x is fixed, r The effect of each unit increase on y, that is, x r The partial regression coefficient on y.

[0157] In this way, the functions of classification, identification and concentration detection of seawater oil spills are realized.

[0158] It should be noted that the detection of characteristic peaks is the initial step of fluorescence-Raman spectroscopy data analysis. Failure to accurately estimate the position of characteristic peaks may cause problems in identifying potential oil products and may lead to erroneous predictions. Therefore, it is very important to accurately estimate the peak parameters such as the position and peak height (light intensity) of characteristic peaks. In the peak detection procedure of this embodiment, three steps of spectrum smoothing, baseline correction, and peak picking are used to improve the accuracy of characteristic peak picking, thereby improving the accuracy of classification and identification of seawater oil spills and concentration detection.

[0159] After the Raman spectrum detection is completed, the automatic control unit controls the common port COM1 of the first three-way valve 11 to be connected to its second selection port NO1, and controls the common ports COM2 and COM4 of the second three-way valve 12 and the fourth three-way valve 14 to be connected to their own first selection ports NC2 and NC4, so as to pump the pipeline cleaning liquid into the pipeline of the automatic circulation platform. By controlling the pumping time, the pumping amount of the pipeline cleaning liquid is adjusted.

[0160] After pumping in an appropriate amount of pipeline cleaning liquid, the automatic control unit controls the common port COM2 of the second three-way valve 12 to communicate with its second selection port NO2 to form a cleaning loop to automatically clean the pipeline of the automatic circulation platform.

[0161] Afterwards, the automatic control unit controls the common port COM4 of the fourth three-way valve 14 to communicate with the second selection port NO4 thereof, so as to clean the quartz cuvette 10 .

[0162] Thus, the automatic cleaning of the pipelines of the automatic circulation platform was completed, preparing for the next oil spill sampling and detection work.

[0163] Of course, the above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A seawater oil spill classification detection device, characterized in that: It includes an automatic circulation platform, an optical detection system and an automatic control unit; among which, The automatic circulation platform is used to collect seawater containing oil spills, and to mix the seawater with nanomaterials required for surface enhanced Raman spectroscopy detection at a constant temperature, and to feed the seawater sample and the constant temperature mixed liquid into the cuvette in a time-sharing manner to perform fluorescence spectroscopy detection and Raman spectroscopy detection respectively; it comprises: --a first three-way valve, wherein the first selection port is used for injecting the nanomaterial, and the second selection port is used for receiving the pipeline cleaning liquid; a second three-way valve, wherein a first selection port thereof is connected to a common port of the first three-way valve; --a constant temperature mixing circulation pipe, the water inlet of which is connected to the common port of the second three-way valve; --A third three-way valve, wherein the first selection port is used for sampling seawater containing spilled oil, and the second selection port is connected to the outlet of the constant temperature mixing circulation pipe; a peristaltic pump, whose water inlet is connected to the common port of the third three-way valve; a fourth three-way valve, wherein the common port thereof is connected to the water outlet of the peristaltic pump, the first selection port thereof is connected to the second selection port of the second three-way valve, and the second selection port of the fourth three-way valve is connected to the cuvette; The automatic control unit performs the following control process on the automatic circulation platform: Control the common port of the third three-way valve to be connected to the first selection port thereof, control the common port of the fourth three-way valve to be connected to the second selection port thereof, start the peristaltic pump, and pump the seawater containing the spilled oil into the cuvette for fluorescence spectrum detection; Control the common ports of the first three-way valve, the second three-way valve and the fourth three-way valve to be connected to the first selection port thereof, control the common port of the third three-way valve to be connected to the second selection port thereof, and pump the nanomaterial into the constant temperature mixing circulation pipe; Control the common port of the second three-way valve to be connected with the second selection port thereof, control the common port of the third three-way valve to be connected with the first selection port thereof, and pump in a certain amount of seawater containing spilled oil; Control the common port of the third three-way valve to communicate with the second selection port of the third three-way valve to form a mixing loop, so that the seawater and the nanomaterial are fully mixed through the constant temperature mixing circulation pipe and kept at a constant temperature to form a constant temperature mixed liquid; Controlling the common port of the fourth three-way valve to communicate with the second selection port thereof, and pumping the constant temperature mixed liquid into the cuvette for Raman spectrum detection; After the Raman spectrum detection is completed, the common port of the first three-way valve is controlled to be connected to the second selection port thereof, and the common ports of the second three-way valve and the fourth three-way valve are controlled to be connected to the first selection port thereof, so as to pump the pipeline cleaning fluid into the pipeline of the automatic circulation platform; Control the common port of the second three-way valve to be connected with the second selection port of the second three-way valve to form a cleaning loop to clean the pipeline of the automatic circulation platform; Controlling the common port of the fourth three-way valve to be connected with the second selection port thereof to clean the cuvette; The optical detection system utilizes a laser light source capable of exciting a fluorescence signal to illuminate a seawater sample in a cuvette to stimulate and collect the fluorescence signal, thereby generating fluorescence spectrum data; or utilizes a laser light source capable of exciting a Raman light signal to illuminate a constant temperature mixed liquid in a cuvette to stimulate and collect the Raman light signal, thereby generating Raman spectrum data; it comprises: --A fluorescence optical path system, comprising a fluorescent laser light source, a first collimating lens, a first narrow-band filter, a first converging lens, a second collimating lens, a first long-wave pass filter, a second converging lens and a fluorescence detector; wherein the fluorescent laser light source is used to emit a 360nm laser, which is processed into parallel light by the first collimating lens, emitted to the first narrow-band filter to eliminate stray light other than 360nm, and then converged to the cuvette through the first converging lens to irradiate the seawater containing oil spill in the cuvette to excite a fluorescent signal; the second collimating lens collects the fluorescent signal, and emits it to the long-wave pass filter as parallel light to filter out interference light of non-fluorescent signals, and then converges to the fluorescent detector through the second converging lens to realize the collection of fluorescent spectrum data; --Raman optical path system, comprising a differential Raman laser, a third collimating lens, a short-wave pass dichroic mirror, a second narrow-band filter, a third narrow-band filter, a first long-wave pass dichroic mirror, a third converging lens, a second long-wave pass dichroic mirror, a second long-wave pass filter, a fourth converging lens and a Raman detector; wherein the differential Raman laser is used to emit 785nm and 830nm lasers, which are processed into parallel light by the third collimating lens and then emitted to the short-wave pass dichroic mirror, and the short-wave pass dichroic mirror is transparent to the 785nm laser and reflects the 830nm laser, so as to form two laser beams for split transmission; wherein the 785nm laser is emitted to the first long-wave pass dichroic mirror after the stray light other than 785nm is filtered out by the second narrow-band filter; the 830nm laser is emitted to the first long-wave pass dichroic mirror; the 785nm laser is emitted to the first long-wave pass dichroic mirror after the stray light other than 785nm is filtered out by the second narrow-band filter; the 830nm laser is emitted to the first long-wave pass dichroic mirror. After the stray light other than 830nm is filtered out by the third narrow-band filter, it is reflected to the first long-wave-pass dichroic mirror through the second long-wave-pass dichroic mirror; the first long-wave-pass dichroic mirror reflects the 785nm laser and transmits the 830nm laser, so that the two laser beams of 785nm and 830nm are converged to the cuvette through the third converging lens to irradiate the constant-temperature mixed liquid in the cuvette to stimulate two Raman light signals of 785nm and 830nm; the two Raman light signals are respectively transmitted to the second long-wave-pass filter through the third converging lens, the first long-wave-pass dichroic mirror and the second long-wave-pass dichroic mirror to filter out non-Raman light signals less than 830nm, and are converged to the Raman detector through the fourth converging lens to realize the collection of Raman spectrum data; The automatic control unit receives the fluorescence spectrum data and the Raman spectrum data, and performs the following seawater oil spill classification detection process: Perform spectral smoothing and noise removal on the fluorescence spectrum data to obtain a smoothed fluorescence spectrum graph; Performing baseline correction on the smoothed fluorescence spectrum to remove the local baseline; Peak picking is performed on the fluorescence spectrum after the local baseline is removed, and the spectral positions and intensities of all characteristic peaks are picked out; The spectral position and intensity of the picked characteristic peak are compared with the fluorescence spectrum of gasoline and diesel to identify whether the spilled oil is gasoline or diesel; When the spilled oil is not gasoline or diesel, performing spectral smoothing and noise removal processing on the Raman spectrum data to obtain a smoothed Raman spectrum graph; Performing baseline correction on the smoothed Raman spectrum to remove the local baseline; Peak picking is performed on the Raman spectrum after the local baseline is removed, and the spectral positions and intensities of all characteristic peaks are picked out; The spectral position and intensity of the picked-up characteristic peaks are compared with the Raman spectra of the PAH types of crude oil and refined oil to identify the PAH types contained in the spilled oil; The type of oil spill can be identified based on the types of PAHs contained in the oil and the proportion of each type of PAHs.

2. The seawater oil spill classification detection device according to claim 1, characterized in that: During Raman spectroscopy detection, The automatic control unit controls the differential Raman laser to emit lasers with wavelengths of 785nm and 830nm, respectively irradiating the constant temperature mixed liquid in the cuvette to stimulate Raman light signals belonging to 785nm and 830nm; The Raman detector collects the Raman light signal of 785nm and the Raman light signal of 830nm to form a Raman characteristic spectrum of 785nm and a Raman characteristic spectrum of 830nm respectively; The automatic control unit makes a difference between the Raman characteristic spectrum at 785 nm and the Raman characteristic spectrum at 830 nm to obtain Raman spectrum data after eliminating fluorescence.

3. The seawater oil spill classification detection device according to claim 1, characterized in that: When the automatic control unit performs smoothing and denoising processing on the Raman spectrum data and the fluorescence spectrum data, the Savitzky-Golay polynomial smoothing algorithm is used to perform spectrum denoising through weighted averaging.

4. The seawater oil spill classification detection device according to claim 3 is characterized in that: The automatic control unit performs the following baseline correction process: The original spectral data P[n] is compared and analyzed with each point in the spectral data E[n] after being smoothed by Savitzky-Golay polynomial. i ] and E[n i ] for comparison, and take the smaller value of the two to generate the baseline curve B[n]; The original spectral data is subtracted from the generated baseline data and the trapezoidal method is used to integrate the data to form a new matrix C[n]; Find the condition that C[n i-1 ] <C[n i-2 ]、C[n i-1 ] <C[n i ] i-1 , extract B[n i-1 ] Generate the minimum baseline B min [n]; The original spectral data P[n] and B min [n] is subtracted to obtain the spectral data D[n] after baseline correction.

5. The seawater oil spill classification detection device according to claim 1, characterized in that: The automatic control unit adopts the following characteristic peak picking process in the process of peak picking of the Raman spectrum and the fluorescence spectrum: The spectral data after denoising and baseline correction is expressed as D[n] = {n1, n2, n3, …, n z }; Every five adjacent data points in the spectral data are grouped into a group of data, denoted as A. k {n i-2 ,n i-1 ,n i ,n i+1 ,n i+2 }, where n i represents the light intensity at the spectral coordinate i; Sort the 5 data points in each set of data in ascending order; If three adjacent sets of data A k-1 , A k , A k+1 A k-1 The spectral coordinates are in ascending order, A k The spectral coordinates of A are out of order. k+1 The spectral coordinates of A are in descending order. k The position is determined as the characteristic peak position.

6. The seawater oil spill classification detection device according to claim 1, characterized in that: The process of the automatic control unit identifying the type of oil spill according to the types of PAHs contained in the oil spill and the proportion of the contents of various PAHs includes: Extract the peak heights of the characteristic peaks corresponding to the five substances of naphthalene, phenanthrene, anthracene, fluoranthene and pyrene in polycyclic aromatic hydrocarbons; Calculating the sum of the peak heights of the five substances to form a total peak height; Calculate the ratio of the sum of the peak heights of the characteristic peaks corresponding to the two substances naphthalene and phenanthrene to the total peak height; If the proportion of naphthalene and phenanthrene is higher than 20%, it is judged as light oil; If the proportion of naphthalene and phenanthrene is between 10% and 20%, it is judged to be fuel oil; If the proportion of naphthalene and phenanthrene is less than 10%, it is judged to be crude oil.

7. The seawater oil spill classification detection device according to any one of claims 1 to 6, characterized in that: After identifying the type of oil spill, the automatic control unit performs an oil spill concentration detection process, including: If the spilled oil is gasoline or diesel, extract all characteristic peak intensities in the fluorescence spectrum; If the spilled oil is not gasoline or diesel, extract all characteristic peak intensities in the Raman spectrum; The following multiple linear regression model was used to calculate the oil spill concentration: y=b0+b1x1+b2x2+…+b r x r +e; Where y represents the oil spill concentration; x1, x2, …, x r represents the intensities of r characteristic peaks extracted from the fluorescence spectrum or Raman spectrum, where r is the total number of characteristic peaks; b0 is a constant term; b1, b2, …, b r is the regression coefficient; e is the random error term.

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