CN112710658A - Aquatic product formaldehyde rapid detection device and method based on visual olfactory fingerprint technology - Google Patents
Aquatic product formaldehyde rapid detection device and method based on visual olfactory fingerprint technology Download PDFInfo
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Abstract
The invention provides an aquatic product formaldehyde rapid detection device based on a visual olfactory fingerprint technology, which comprises an upper computer, an image acquisition chamber, a camera bracket, a camera, a plane diffuse reflection light source, a reaction chamber, a color sensitive sensor, a gas collection chamber, a pump, a nitrogen cylinder, an organic absorption cell, an inorganic absorption cell, a gas inlet pipeline and a gas outlet pipeline; the device comprises a plane diffuse reflection light source, a reaction chamber, a color sensitive sensor and an image acquisition chamber, wherein the plane diffuse reflection light source is arranged at the bottom of the inner side of the image acquisition chamber; the camera is arranged right above the reaction chamber through a camera bracket and is connected with an external upper computer through a data line; the gas collection chamber and the nitrogen cylinder are connected with a pump through pipelines, the pump is connected with one end of the reaction chamber through a gas inlet pipeline, and the other end of the reaction chamber is sequentially connected with the organic absorption pool and the inorganic absorption pool through a gas outlet pipeline. The method is simple to operate, high in detection speed, low in cost and environment-friendly, and can be used for quickly detecting the formaldehyde content in various links of aquatic products.
Description
Technical Field
The invention relates to a method and a device for quickly detecting formaldehyde in aquatic products, in particular to a device and a method for quickly detecting formaldehyde in aquatic products based on a visual olfactory fingerprint technology, and belongs to the technical field of agricultural product detection.
Background
The aquatic product is delicious in taste, is rich in various nutritional ingredients such as high-quality protein, unsaturated fatty acid, vitamins and minerals, and is deeply loved by consumers. However, as the aquatic products have high water content, the muscle tissues are fragile, endogenous protease is active, and protein is easy to degrade in the storage process, so that the aquatic products are rotten and deteriorated, some illegal vendors use formaldehyde to carry out preservative treatment on the aquatic products such as squid and the like in order to prolong the shelf life of the products, and the squid treated by the formaldehyde is not easy to rot due to the fact that the protein is solidified, the water holding rate is improved, the storage life is prolonged, and the squid is expanded and shaped after absorbing water, so that the volume is increased, the quality is increased, and the appearance is bright and beautiful. However, formaldehyde is a strong carcinogen, and can cause abnormal olfactory, pulmonary, hepatic and immune functions, dizziness, cough, nausea, vomiting, abdominal pain, coma, shock, bleeding, renal failure and death. Therefore, the formaldehyde content of the aquatic products before the aquatic products come into the market needs to be accurately detected so as to ensure the food quality safety and strictly attack the behavior of illegally treating the aquatic products.
The traditional detection methods for formaldehyde in aquatic products mainly comprise spectrophotometry, electrochemistry, chromatography and the like, and although the methods have high sensitivity and accurate measurement results, the methods have various defects of long detection time, high detection cost, complex pretreatment and the like to different degrees. As the determination method of the formaldehyde content in the aquatic products specified by the current standard SC/T3025-2006, the formaldehyde in the aquatic products needs to be extracted by distillation, the steps are complicated, the time is consumed, and the method is difficult to be used for on-site rapid detection; the invention patent with the patent application number of 201510789129.X discloses a method for detecting the formaldehyde content in a spanish mackerel, which has low detection cost, can effectively extract and detect the formaldehyde in the spanish mackerel, but still needs operation steps of pretreatment, extraction, essence, oxidation reaction, titration and the like, the pretreatment is complex, and the detection period is long; the invention patent with the patent application number of 201310371538.9 discloses a method for rapidly detecting volatile formaldehyde by surface enhanced Raman spectroscopy, which is more convenient and rapid compared with the traditional method, however, in the detection process of the method, a sample needs to be crushed, and the spectrum is measured by Raman enhancement technology after derivatization reaction, so that the operation is very complicated, and in addition, the equipment cost is higher, and the method is not beneficial to popularization and use. Therefore, a method for detecting aquatic product formaldehyde with high detection speed, few steps and low cost is urgently needed to adapt to the development trend of the aquatic product market and improve the protection of food safety.
Disclosure of Invention
The invention aims to provide a device and a method for rapidly detecting formaldehyde in aquatic products based on a visual olfactory fingerprint technology.
The technical solution of the invention is as follows: the aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology structurally comprises an upper computer, an image acquisition chamber, a camera bracket, a camera, a plane diffuse reflection light source, a reaction chamber, a color sensitive sensor, a gas collection chamber, a pump, a nitrogen cylinder, an organic absorption cell, an inorganic absorption cell, an air inlet pipeline and an air outlet pipeline; the image acquisition chamber is of a square closed box-shaped structure and made of stainless steel, and the inner surface of the image acquisition chamber is coated with a black diffuse reflection coating; the plane diffuse reflection light source is arranged at the bottom of the inner side of the image acquisition chamber, the reaction chamber is arranged on the upper surface of the plane diffuse reflection light source, and the color sensitive sensor is arranged on the upper surface of the reaction chamber; the camera is arranged right above the reaction chamber through a camera bracket and is connected with an external upper computer through a data line; the gas collection chamber and the nitrogen cylinder are connected with a pump through pipelines, the pump is connected with one end of the reaction chamber through a gas inlet pipeline, and the other end of the reaction chamber is sequentially connected with the organic absorption pool and the inorganic absorption pool through a gas outlet pipeline.
Furthermore, the front end of the reaction chamber is pointed, the rear end of the reaction chamber is blunt, and corners inside the reaction chamber are rounded corners; the reaction chamber is provided with a reaction chamber, a gas inlet, a main flow dividing baffle plate, a plurality of rows of auxiliary flow dividing baffle plates and a plurality of rows of auxiliary flow dividing baffle plates, wherein the gas inlet is arranged at the front end of the reaction chamber and is connected with a gas inlet pipeline; the color-sensitive sensor placing groove is arranged at the bottom of the space at the rear side of the auxiliary flow dividing baffle, is used for installing a color-sensitive sensor and is arranged corresponding to a lens of a camera; quartz glass light-transmitting openings are formed in the top, the bottom and the two sides of the color-sensitive sensor placing groove; the movable reaction chamber upper cover is arranged at the top of the reaction chamber, and the image acquisition window is arranged on the surface of the reaction chamber upper cover and corresponds to the color-sensitive sensor placing groove; the gas outlet is arranged at the rear end of the reaction chamber and is connected with a gas outlet pipeline.
Further, the preparation method of the color-sensitive sensor comprises the following steps: selecting the following color sensitive materials: ZnTPP, MnTPP, CuTPP, NiTPP, CoTPP, neutral red, bromophenol blue, bromocresol green and methyl red are respectively dissolved by chloroform solvent, the neutral red, the bromophenol blue, the bromocresol green and the methyl red are dissolved by ethanol and mixed to obtain color sensitive material solution with the concentration of 1 mg/mL, the solution is absorbed by a sample application capillary tube and is printed on a hydrophobic polyvinylidene fluoride film, and the color sensitive material sensor array is prepared by volatilizing the solvent in nitrogen environment.
Further, a mixed solution of methanol and water is filled in the organic absorption cell, wherein the mass ratio of the methanol to the water is 70: 30; the inside of the inorganic absorption tank is filled with hydrochloric acid solution with the concentration of 0.12mol/L, a pipeline is arranged at an air outlet of the inorganic absorption tank, and NaHCO is filled in the pipeline3And (3) granules.
A method for rapidly detecting aquatic product formaldehyde based on a visual olfactory fingerprint technology specifically comprises the following steps:
1) before the detection is started, the whole device is placed in a thermostatic chamber, so that the detection result is not influenced by the temperature; opening the upper computer and the camera, and simultaneously opening the plane diffuse reflection light source, wherein the light source uniformly irradiates the surface of the color-sensitive sensor through quartz glass light-transmitting openings at the top, the bottom and two sides of the reaction chamber, so that the light intensity of color-sensitive materials on the color-sensitive sensor is ensured to be consistent, and the influence of background noise of an image system is reduced;
2) opening an upper cover of the reaction chamber, placing the color-sensitive sensors on a color-sensitive sensor placing groove of the reaction chamber, obtaining R, G, B three-component images of the color-sensitive sensors before and after reaction through an image acquisition window at the upper end of the reaction chamber by a camera, transmitting the R, G, B three-component images to an upper computer, and carrying out image processing by the upper computer to obtain initial color information;
3) when a sample is detected, the sample is placed in the gas collection chamber, the pump is started, volatile gas generated by the sample is pumped into the reaction chamber from the gas inlet of the gas inlet pipeline through the pump, and uniform zonal airflow is formed under the shunting action of the main shunting baffle and the auxiliary shunting baffle; the uniformly mixed air flow is in contact reaction with the color-sensitive sensors on the color-sensitive sensor placing grooves, the cameras acquire R, G, B images of the color-sensitive sensors after reaction and transmit the R, G, B images to the upper computer, and the upper computer performs image processing to obtain color information of the sample;
4) the reacted volatile gas enters an air outlet pipeline from an air outlet, then sequentially passes through an organic absorption pool and an inorganic absorption pool, absorbs harmful substances and then is discharged into the atmosphere; after the sample detection is finished, opening a switch of a nitrogen bottle, filling nitrogen into the whole gas path, so that the gas in the whole gas path is replaced, the system initialization is finished, and the next sample is continuously detected;
5) after all samples are detected, characteristic variables of 5 main components before and after the color change value of the color sensitive sensor is reacted are used as input variables of an error back propagation artificial neural network model BP-ANN, the content of formaldehyde in the samples is used as output variables, a cross validation root mean square error is used as an evaluation standard of network training, the prediction effect of the root mean square error value evaluation model is predicted, and the correlation between a predicted value and an actual measurement value is evaluated by using a training set correlation coefficient Rc and a prediction set correlation coefficient Rp.
Compared with the prior art, the invention has the advantages that:
1) the rapid detection device for formaldehyde in aquatic products provided by the invention has good compatibility, can detect various aquatic product sample objects such as squid, sea cucumber, shrimp meat and the like, and can quantitatively detect the content of formaldehyde in the aquatic products; compared with the existing method for detecting formaldehyde in aquatic products, the device has the advantages of light structure, simple operation, quick and nondestructive detection method, no need of complicated pretreatment procedures such as distillation and derivation, low cost, environmental friendliness and capability of being used for quickly detecting the formaldehyde content in various links such as purchasing, transporting, selling and storing of aquatic products;
2) the reaction chamber of the detection device is provided with the main shunting baffle and the auxiliary shunting baffle, so that the uniformity of volatile gas contacting with the color-sensitive sensor can be ensured; the relative position of the camera and the color sensitive sensor is ensured to be fixed by arranging the color sensitive sensor placing groove and the camera bracket; the planar diffuse reflection light source at the bottom can ensure the uniformity of the luminosity of the color-sensitive sensor and ensure the image uniformity of the color-sensitive sensor of the reactor; the quartz glass light-transmitting openings at the two sides, the top and the bottom can meet the requirements of polishing from different angles; the corners in the reaction chamber use fillets, so that gas residue buffering of the reaction chamber is reduced; the whole frame of the device is made of stainless steel, so that gas adsorption is effectively reduced;
3) the detection device is provided with the organic absorption tank and the inorganic absorption tank, the organic absorption tank can effectively absorb organic reagents such as formaldehyde and the like in volatile gas, the inorganic absorption tank can effectively absorb amine substances and water vapor in aquatic products, tail gas is ensured to be discharged harmlessly, and the detection device is green, environment-friendly and eco-friendly.
Drawings
FIG. 1 is a schematic structural diagram of an aquatic product formaldehyde rapid detection device based on a visible olfactory fingerprint technology.
FIG. 2 is a schematic diagram of the structure of the reaction chamber.
In the figure, 1 is an upper computer, 2 is an image acquisition chamber, 3 is a camera bracket, 4 is a camera, 5 is a plane diffuse reflection light source, 6 is a reaction chamber, 7 is a color-sensitive sensor, 8 is a gas collection chamber, 9 is a pump, 10 is a nitrogen bottle, 11 is an organic absorption pool, 12 is an inorganic absorption pool, 13 is a main flow dividing baffle, 14 is an auxiliary flow dividing baffle, 15 is a color-sensitive sensor placing groove, 16 is a reaction chamber upper cover, 17 is an image acquisition window, 18 is a quartz glass light transmission opening, 19 is an air inlet, 20 is an air outlet, 21 is an air inlet pipeline, and 22 is an air outlet pipeline.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings. Examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside" and "outside" indicate the orientation or positional relationship based on the content of the drawings in the specification, which is only for convenience of describing the structural relationship of the present invention, and does not limit or imply that the device or element to be referred to must be disposed only in a specific orientation or be configured in a specific configuration, so the present invention is not limited thereto.
In the present invention, unless otherwise specifically stated or limited, the terms "mounted," "connected," and "fixed" are to be construed broadly, for example: can be fixedly connected or detachably connected; can be directly connected or indirectly connected through an intermediate medium; either internally or in interactive relation. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
As shown in fig. 1, the aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology structurally comprises an upper computer 1, an image acquisition chamber 2, a camera support 3, a camera 4, a planar diffuse reflection light source 5, a reaction chamber 6, a color sensitive sensor 7, a gas collection chamber 8, a pump 9, a nitrogen cylinder 10, an organic absorption pool 11, an inorganic absorption pool 12, an air inlet pipeline 21 and an air outlet pipeline 22; the whole image acquisition chamber 2 is of a square closed box-shaped structure, and the planar diffuse reflection light source 5 is arranged at the bottom of the inner side of the image acquisition chamber 2, so that the uniformity of the luminosity of the color-sensitive sensor 7 can be ensured, and the uniformity of an image obtained by the color-sensitive sensor 7 can be ensured; the reaction chamber 6 is arranged on the upper surface of the plane diffuse reflection light source 5, and the color sensitive sensor 7 is arranged on the upper surface of the reaction chamber 6; the camera 4 is arranged right above the reaction chamber 6 through the camera bracket 3, is connected with an external upper computer 1 through a data line and is used for controlling image acquisition and data processing; the gas collection chamber 8 and the nitrogen cylinder 10 are simultaneously connected with a pump 9 through pipelines, the pump 9 is connected with one end of the reaction chamber 6 through an air inlet pipeline 21, and the other end of the reaction chamber 6 is sequentially connected with an organic absorption pool 11 and an inorganic absorption pool 12 through an air outlet pipeline 22.
As shown in fig. 2, the front end of the reaction chamber 6 is pointed, the rear end is blunt, and corners inside the reaction chamber 6 are rounded corners for reducing gas residue buffering inside the reaction chamber 6; the structure of the device comprises a main shunting baffle 13, an auxiliary shunting baffle 14, a color sensitive sensor placing groove 15, a reaction chamber upper cover 16, an image acquisition window 17, a quartz glass light-transmitting opening 18, a gas inlet 19 and a gas outlet 20; the gas inlet 19 is arranged at the front end of the reaction chamber 6 and is connected with the gas inlet pipeline 21, the main diversion baffle 13 is arranged at the rear side of the gas inlet 19, and the auxiliary diversion baffles 14 are arranged at the rear side of the main diversion baffle 13 in parallel, so that a strip-shaped stable gas flow can be formed, the uniformity of a flow field of the reaction chamber is better, and the uniformity of volatile gas contacting with the color-sensitive sensor 7 is ensured; the color-sensitive sensor placing groove 15 is arranged at the bottom of the rear space of the auxiliary shunt baffle 14, is used for installing the color-sensitive sensor 7, and is arranged corresponding to the lens of the camera 4 to ensure that the relative position of the camera 4 and the color-sensitive sensor 7 is fixed; quartz glass light-transmitting openings 18 are formed in the top, the bottom and the two sides of the color-sensitive sensor placing groove 15, so that the requirements of polishing from different angles can be met; the movable reaction chamber upper cover 16 is arranged at the top of the reaction chamber 6, and the image acquisition window 17 is arranged on the surface of the reaction chamber upper cover 16 and corresponds to the color-sensitive sensor placing groove 15; the air outlet 20 is arranged at the rear end of the reaction chamber 6 and is connected with an air outlet pipeline 22.
The image acquisition room 2 adopts stainless steel material effectively to reduce gas adsorption, and its internal surface all scribbles black diffuse reflection coating, guarantees that plane diffuse reflection light source 5 is even luminous not reveal, also guarantees simultaneously that the internal environment does not receive external light source influence.
The preparation method of the color-sensitive sensor 7 comprises the following steps: selecting color sensitive materials which are sensitive to formaldehyde in aquatic products, such as 5, 10, 15, 20-Tetraphenyl-21H, 23H-porphine zinc (ZnTPP, tetraphenylporphyrin zinc), 5, 10, 15, 20-Tetraphenyl-21H, 23H-porphine mangnase (MnTPP, tetraphenylporphyrin manganese), 5, 10, 15, 20-Tetraphenyl-21H, 23H-porphine copperr (CuTPP, tetraphenylporphyrin copper), 5, 10, 15, 20-Tetraphenyl-21H, 23H-porphine nickel (NiTPP, tetraphenylporphyrin nickel) and 5, 10, 15, 20-Tetraphenyl-21H, 23H-porphine cobalt (CoTPP, tetraphenylporphyrin cobalt); and indicators such as neutral red, phenol blue, bromocresol green and methyl red are also included. Respectively dissolving ZnTPP, MnTPP, CuTPP, NiTPP and CoTPP in a trichloromethane solvent, and dissolving neutral red, carvacrol blue, bromocresol green and methyl red in ethanol to obtain color sensitive material solutions with the concentration of 1 mg/mL, absorbing the solutions by a sample application capillary tube, printing the solutions on a hydrophobic polyvinylidene fluoride (PVDF) membrane, and preparing the color sensitive material sensor array by volatilizing the solvent in a nitrogen environment.
The organic absorption pool 11 is filled with a mixed solution (the mass ratio is 70: 30) of methanol and water, organic reagents such as formaldehyde in volatile gas can be effectively absorbed, and the inorganic absorption pool 12 is filled with a hydrochloric acid solution with the concentration of 0.12mol/L, so that volatile amine substances in aquatic products can be effectively absorbed; of inorganic absorption cells 12NaHCO is arranged in the gas outlet pipeline3And the particles are filled for absorbing acid and water vapor in the pipeline.
The method for rapidly detecting the formaldehyde in the aquatic products based on the visible olfactory fingerprint technology by using the device specifically comprises the following steps:
1) before the detection is started, the whole device is placed in a thermostatic chamber, so that the detection result is not influenced by the temperature; the upper computer 1 and the camera 4 are turned on, the plane diffuse reflection light source 5 is turned on at the same time, the light source penetrates through quartz glass light-transmitting openings 18 at the top, the bottom and two sides of the reaction chamber 6 and uniformly irradiates the surface of the color-sensitive sensor 7, the light intensity of the color-sensitive material on the color-sensitive sensor 7 is ensured to be consistent, and the influence of background noise of an image system is reduced;
2) opening the upper cover 16 of the reaction chamber, placing the color-sensitive sensor 7 on the color-sensitive sensor placing groove 15 of the reaction chamber 6, obtaining R, G, B three-component images of the color-sensitive sensor 7 before and after reaction by the camera 4 through an image acquisition window 17 at the upper end of the reaction chamber 6, transmitting the obtained images to the upper computer 1, and carrying out image processing on the upper computer 1 to obtain initial color information;
3) when a sample is detected, the sample is placed in the gas collection chamber 8, the pump 9 is started, volatile gas generated by the sample is pumped into the reaction chamber 6 from the gas inlet 19 of the gas inlet pipeline 21 through the pump 9, and uniform zonal gas flow is formed under the shunting action of the main shunting baffle 13 and the auxiliary shunting baffle 14; the uniformly mixed air flow is in contact reaction with the color-sensitive sensor 7 on the color-sensitive sensor placing groove 15, the camera 4 obtains R, G, B images of the color-sensitive sensor 7 after reaction and transmits the images to the upper computer 1, and the upper computer 1 performs image processing to obtain sample color information;
4) the reacted volatile gas enters an air outlet pipeline 22 from an air outlet 20, then sequentially passes through an organic absorption pool 11 and an inorganic absorption pool 12, absorbs harmful substances and then is discharged into the atmosphere; after the sample detection is finished, opening a switch of the nitrogen cylinder 10, filling nitrogen into the whole gas path, so that the gas in the whole gas path is replaced, the system initialization is finished, and the next sample is continuously detected;
5) after all the samples are detected, the characteristic variables of the 5 main components before and after the color change value of the color sensitive sensor 7 reacts are used as input variables of an error back propagation artificial neural network model BP-ANN, the content of formaldehyde in the samples is used as output variables, the cross validation root mean square error is used as an evaluation standard of network training, the prediction effect of the model is evaluated by predicting the root mean square error value, and the correlation between a predicted value and an actual measurement value is evaluated by using a training set correlation coefficient Rc and a prediction set correlation coefficient Rp.
The following examples further illustrate the practice of the present invention.
Examples
The quick detection process of formaldehyde in squid based on the visual smell fingerprint technology specifically operates as follows:
1) randomly purchasing 60 fresh squids in a local supermarket;
2) sampling each squid and randomly dividing into 6 groups, wherein one group is set as a blank group, and the squid sample can be separated without water washing and is marked as S-0; soaking the other 5 groups of squid samples in formaldehyde solutions with different concentrations (1%, 2%, 4%, 6%, 8%) for 12 hours respectively, marking as S-1, S-2, S-3, S-4 and S-5 respectively, and 10 samples with each concentration;
3) dissolving ZnTPP, MnTPP, CuTPP, NiTPP and CoTPP by using a trichloromethane solvent, dissolving neutral red, carvacrol blue, bromocresol green and methyl red by using ethanol, mixing to obtain a solution with the concentration of each color sensitive material being 1 mg/mL, absorbing the solution by a sample application capillary tube, printing and dyeing the solution on a hydrophobic polyvinylidene fluoride (PVDF) membrane, and preparing a color sensitive material sensor array by volatilizing the solvent in a nitrogen environment;
4) placing the prepared color-sensitive sensor array on a color-sensitive sensor placing groove at the bottom of the reaction chamber, uniformly polishing a bottom diffuse reflection light source from the bottom, and obtaining an image of the color-sensitive sensor array before reaction by a camera above the color-sensitive sensor placing groove;
5) putting a squid sample in the gas collection chamber, starting a pump, pumping volatile gas of the squid sample into the reaction chamber to enter the reaction chamber to be in contact reaction with the color-sensitive sensors on the color-sensitive sensor placing grooves, and acquiring an image of the color-sensitive sensor array after the reaction by using a camera above the color-sensitive sensor placing grooves;
6) processing the sensor array images before and after the reaction by the upper computer to obtain a reaction difference value before and after the reaction of the color-sensitive sensor and the sleeve-fish sample;
7) volatile gas of the squid sample from the reaction chamber sequentially enters the organic absorption pool and the inorganic absorption pool and is finally discharged into the air;
8) the method is characterized in that characteristic variables of the first 5 main components of color change values before and after reaction of a color-sensitive gas sensor are used as input variables of an error back propagation artificial neural network model (BP-ANN), the content of formaldehyde in the squid is used as output variables, the method is verified, the model uses a cross verification root mean square error as an evaluation standard of network training, the prediction effect of the model is evaluated by a prediction root mean square error value, and the correlation between a predicted value and an actual measurement value is evaluated by a training set correlation coefficient Rc and a prediction set correlation coefficient Rp. The result shows that the relevance of the formaldehyde content in the squid detected based on the visual olfactory fingerprint technology and the actual formaldehyde content in the squid is good, Rc =1 and Rp =0.9887, and in order to verify the accuracy and the applicability of the model, a paired sample t test is used for verifying the pairwise difference between the predicted value and the actual addition amount of the formaldehyde in the BP-ANN model. As can be seen from Table 1, the Sig values in both the training and prediction sets were greater than 0.05, and thus there was no significant difference between the predicted and actual values for the model.
TABLE 1 paired sample t test results
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A fast aquatic product formaldehyde detection device based on a visual olfactory fingerprint technology structurally comprises an upper computer (1), an image acquisition chamber (2), a camera support (3), a camera (4), a planar diffuse reflection light source (5), a reaction chamber (6), a color sensitive sensor (7), a gas collection chamber (8), a pump (9), a nitrogen cylinder (10), an organic absorption pool (11), an inorganic absorption pool (12), an air inlet pipeline (21) and an air outlet pipeline (22); the device is characterized in that the whole image acquisition chamber (2) is of a square closed box-shaped structure, the planar diffuse reflection light source (5) is arranged at the bottom of the inner side of the image acquisition chamber (2), the reaction chamber (6) is arranged on the upper surface of the planar diffuse reflection light source (5), and the color-sensitive sensor (7) is arranged on the upper surface of the reaction chamber (6); the camera (4) is arranged right above the reaction chamber (6) through the camera bracket (3) and is connected with an external upper computer (1) through a data line; the gas collection chamber (8) and the nitrogen cylinder (10) are simultaneously connected with the pump (9) through a pipeline, the pump (9) is connected with one end of the reaction chamber (6) through an air inlet pipeline (21), and the other end of the reaction chamber (6) is sequentially connected with the organic absorption pool (11) and the inorganic absorption pool (12) through an air outlet pipeline (22).
2. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the front end of the reaction chamber (6) is pointed, the rear end is blunt, and corners inside the reaction chamber (6) use round corners.
3. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the reaction chamber (6) comprises a main shunting baffle (13), an auxiliary shunting baffle (14), a color-sensitive sensor placing groove (15), a reaction chamber upper cover (16), an image acquisition window (17), a quartz glass light transmission opening (18), an air inlet (19) and an air outlet (20); wherein the air inlet (19) is arranged at the front end of the reaction chamber (6) and is connected with the air inlet pipeline (21), the main shunting baffle (13) is arranged at the rear side of the air inlet (19), and a plurality of rows of auxiliary shunting baffles (14) are arranged at the rear side of the main shunting baffle (13) in parallel; the color-sensitive sensor placing groove (15) is arranged at the bottom of the rear space of the auxiliary flow dividing baffle (14), is used for installing the color-sensitive sensor (7) and is arranged corresponding to the lens of the camera (4); quartz glass light-transmitting openings (18) are formed in the top, the bottom and two sides of the color-sensitive sensor placing groove (15); the movable reaction chamber upper cover (16) is arranged at the top of the reaction chamber (6), and the image acquisition window (17) is arranged on the surface of the reaction chamber upper cover (16) and corresponds to the color-sensitive sensor placing groove (15); the air outlet (20) is arranged at the rear end of the reaction chamber (6) and is connected with an air outlet pipeline (22).
4. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the image acquisition chamber (2) is made of stainless steel, and the inner surface of the image acquisition chamber is coated with a black diffuse reflection coating.
5. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the preparation method of the color sensitive sensor (7) is as follows: selecting the following color sensitive materials: ZnTPP, MnTPP, CuTPP, NiTPP, CoTPP, neutral red, bromophenol blue, bromocresol green and methyl red are respectively dissolved by chloroform solvent, the neutral red, the bromophenol blue, the bromocresol green and the methyl red are dissolved by ethanol and mixed to obtain color sensitive material solution with the concentration of 1 mg/mL, the solution is absorbed by a sample application capillary tube and is printed on a hydrophobic polyvinylidene fluoride film, and the color sensitive material sensor array is prepared by volatilizing the solvent in nitrogen environment.
6. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the organic absorption cell (11) is filled with a mixed solution of methanol and water, wherein the mass ratio of methanol to water is 70: 30.
7. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein the inorganic absorption cell (12) is filled with 0.12mol/L hydrochloric acid solution.
8. The aquatic product formaldehyde rapid detection device based on the visual olfactory fingerprint technology as claimed in claim 1, wherein a pipeline filled with NaHCO is arranged at an air outlet of the inorganic absorption tank (12)3And (3) granules.
9. The method for rapidly detecting the formaldehyde in the aquatic products based on the visible olfactory fingerprint technology by using the device for rapidly detecting the formaldehyde in the aquatic products based on the visible olfactory fingerprint technology as claimed in claim 1 comprises the following steps:
1) before the detection is started, the whole device is placed in a thermostatic chamber, so that the detection result is not influenced by the temperature; opening the upper computer (1) and the camera (4), simultaneously opening the plane diffuse reflection light source (5), and uniformly irradiating the light source on the surface of the color-sensitive sensor (7) through quartz glass light-transmitting openings (18) at the top, the bottom and two sides of the reaction chamber (6), so as to ensure the light intensity of the color-sensitive material on the color-sensitive sensor (7) to be consistent and reduce the background noise influence of an image system;
2) opening an upper cover (16) of the reaction chamber, placing the color-sensitive sensor (7) on a color-sensitive sensor placing groove (15) of the reaction chamber (6), obtaining R, G, B three-component images of the color-sensitive sensor (7) before and after reaction by the camera (4) through an image acquisition window (17) at the upper end of the reaction chamber (6), transmitting the obtained images to the upper computer (1), and carrying out image processing on the upper computer (1) to obtain initial color information;
3) when a sample is detected, the sample is placed in the gas collection chamber (8), the pump (9) is opened, volatile gas generated by the sample is pumped into the reaction chamber (6) from the gas inlet (19) of the gas inlet pipeline (21) through the pump (9), and uniform zonal gas flow is formed under the shunting action of the main shunting baffle (13) and the auxiliary shunting baffle (14); the uniformly mixed air flow is in contact reaction with a color-sensitive sensor (7) on a color-sensitive sensor placing groove (15), a camera (4) obtains R, G, B images of the color-sensitive sensor (7) after the reaction and transmits the R, G, B images to an upper computer (1), and the upper computer (1) performs image processing to obtain color information of a sample;
4) the reacted volatile gas enters an air outlet pipeline (22) from an air outlet (20), then sequentially passes through an organic absorption pool (11) and an inorganic absorption pool (12), absorbs harmful substances and then is discharged into the atmosphere; after the sample detection is finished, opening a switch of a nitrogen gas bottle (10), filling nitrogen gas into the whole gas path, so that the gas in the whole gas path is replaced, the system initialization is finished, and the next sample is continuously detected;
5) after all samples are detected, characteristic variables of the 5 main components before and after the color change value of the color sensitive sensor (7) reacts are used as input variables of an error back propagation artificial neural network model BP-ANN, the content of formaldehyde in the samples is used as output variables, a cross validation root mean square error is used as an evaluation standard of network training, the prediction effect of the model is evaluated by a prediction root mean square error value, and the correlation between a predicted value and an actually measured value is evaluated by a training set correlation coefficient Rc and a prediction set correlation coefficient Rp.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114199861A (en) * | 2021-11-24 | 2022-03-18 | 中国汽车技术研究中心有限公司 | Electronic nose and method for detecting low-concentration water-containing gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114199861A (en) * | 2021-11-24 | 2022-03-18 | 中国汽车技术研究中心有限公司 | Electronic nose and method for detecting low-concentration water-containing gas |
| CN114199861B (en) * | 2021-11-24 | 2024-04-26 | 中国汽车技术研究中心有限公司 | Electronic nose and method for detecting low-concentration water-containing gas |
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