Smell traceability model establishment method

Abstract

The invention discloses a smell traceability model establishment method, and relates to the technical field of detection, and the method comprises the following steps: collecting to-be-detected volatile gas by using a trapping tube; desorbing the volatile gas to be detected, and then separating to obtain the separated volatile gas; respectively and simultaneously carrying out qualitative and quantitative detection and olfactory identification test on the separated volatile gas; associating a qualitative and quantitative detection result with a smell identification test result, and establishing a smell traceability model; wherein the trapping pipe comprises a first section, a second section and a third section which are arranged in sequence, the material of an adsorbent of the first section comprises quartz wool, the material of an adsorbent of the second section comprises a high-molecular linear polymer, and the material of an adsorbent of the third section comprises graphitized carbon black. The enriched volatile organic compounds are desorbed and then subjected to qualitative and quantitative detection and olfactory identification test, so that the sensory characteristics, properties and contents of the odor substances can be associated, and the establishment of an odor traceability model is realized.

Description

Technical Field

[0001] The present application relates to the field of detection technology, and in particular to a method for establishing an odor tracing model. Background Art

[0002] Driven by the need for lightweight vehicles, polymer materials are increasingly being used in automotive interiors. However, these polymers release volatile organic compounds (VOCs) when exposed to sunlight and high temperatures. Due to the prolonged confinement of vehicles, these compounds can lead to unpleasant odors within the vehicle. Odor perception is one of the most intuitive psychological experiences of the human body, and more and more people are beginning to consider in-car odor as a factor in their vehicle quality assessment. Therefore, for automakers, accurately identifying the source of odors and addressing them is crucial for effectively improving vehicle odor quality assessments. However, in-car odors are a combination of multiple odorants, making it impossible to distinguish and accurately trace odors based solely on subjective perception. Summary of the Invention

[0003] This application provides a method for establishing an odor tracing model to solve the existing problem of being unable to distinguish and accurately trace odors.

[0004] In a first aspect, the present application provides a method for establishing an odor tracing model, comprising the following steps:

[0005] Use a capture tube to collect the volatile gas to be tested;

[0006] Desorbing and separating the volatile gas to be measured to obtain the separated volatile gas;

[0007] The separated volatile gases are subjected to qualitative and quantitative detection and olfactory testing simultaneously;

[0008] Correlate the qualitative and quantitative test results with the olfactory identification test results to establish an odor tracing model;

[0009] The collecting tube includes a first section, a second section and a third section arranged in sequence. The adsorbent material of the first section includes quartz wool, the adsorbent material of the second section includes a high molecular linear polymer, and the adsorbent material of the third section includes graphitized carbon black.

[0010] In the present application, the capture tube includes a first section, a second section and a third section arranged in sequence. The material of the adsorbent in the first section includes quartz wool, the material of the adsorbent in the second section includes a high molecular linear polymer, and the material of the adsorbent in the third section includes graphitized carbon black. The quartz wool mainly promotes the recovery of semi-volatile substances (substances after C22). The high molecular linear polymer in the middle section is a weak adsorbent with the characteristics of high thermal stability, antioxidant, and low adsorption of water. The adsorption principle mainly relies on the intermolecular interaction between the π electrons in the molecules and the lone electron pairs on the ether oxygen atoms and the adsorbed substances; the high molecular linear polymer has good adsorption performance for most substances with medium and high boiling points (boiling point of 50-260°C, test conditions of 20°C, 0.1-4kPa), and is suitable for the enrichment of volatile organic compounds of C6 to C26, but has poor adsorption performance for small molecular substances with low boiling points. Back-end graphitized carbon black is a strong adsorbent that can be used for the adsorption and enrichment of C4-C20 volatile compounds. The enrichment mainly relies on the induction and dispersion effects of the plane of the graphite crystal on the adsorbed substances, and has a broad spectrum of adsorption properties. This application uses multi-stage adsorbents to adjust the adsorbent substances from the most retained to the least retained, effectively expanding the range of adsorbable volatiles, achieving adsorption of volatile substances from 1,3-butadiene to C30, increasing the adsorption range of target analytes, and improving the accuracy of analysis. After desorption, the enriched volatile organic compounds are subjected to qualitative and quantitative detection and olfactory testing, which can associate the sensory characteristics of the odor substances with their properties and content, and realize the establishment of an odor tracing model. The odor tracing model can be used to trace the source of unknown odors and quickly find the source of the odor. The odor intensity and properties obtained from the olfactory test are analyzed in correspondence with the qualitative and quantitative spectra, and the source of the odor substances in the vehicle can be traced back. Ultimately, by adjusting the material formula and production process, the odor is improved step by step from materials to parts to the entire vehicle, achieving the goal of targetedly solving the source of the odor in the vehicle.

[0011] It should be noted that, usually the first section is the front section of the collection tube in the collection direction, the second section is the middle section of the collection tube in the collection direction, and the third section is the last section of the collection tube in the collection direction. With this arrangement, the gas passes through the front section of the collection tube in turn, and the semi-volatile substances (substances after C22) in the gas are adsorbed by the quartz wool; then enters the middle section, and the volatile organic compounds of C6 to C26 in the gas are adsorbed by the high molecular linear polymer; then enters the last section, and the small molecular substances in the gas are adsorbed by graphitized carbon black, thereby effectively expanding the range of adsorbable volatile substances and realizing the adsorption of volatile substances from 1,3-butadiene to C30.

[0012] In some embodiments, the high molecular weight linear polymer includes at least one of Tenax GC, Tenax TA, and Tenax GR. Using at least one of the above high molecular weight linear polymers can improve the enrichment of C6-C26 volatile organic compounds. Tenax GC is poly-2,6-diphenyl ether, Tenax TA is 2,6-diphenylfuran, and Tenax GR is composed of 70% Tenax TA and 30% graphitized carbon black; and / or,

[0013] The graphitized carbon black includes at least one of Carbograph 5TD, Carbopack X, Carbopack B, Carbotrap, and ENVICarb SPE. Using at least one of these graphitized carbon blacks can improve the adsorption and enrichment of C4-C20 volatile compounds. Carbograph 5TD is primarily composed of graphitized carbon. Carbopack X is a black carbon-based adsorbent. Carbopack B is a black fine-particle carbon adsorbent. Carbotrap is a carbon-based adsorbent. ENVICarb SPE is a solid phase extraction (SPE) carbon adsorbent.

[0014] In some embodiments, the particle size of the adsorbent material of the second stage is 0.18 mm to 0.25 mm. The particle size of the adsorbent material of the second stage within this range can further improve the enrichment of C6 to C26 volatile organic compounds; and / or,

[0015] The particle size of the adsorbent material in the third stage is 0.42 mm to 0.64 mm. The particle size of the adsorbent material in the third stage within this range can further improve the enrichment of C4 to C20 volatile organic compounds; and / or,

[0016] The length of the first section is 3 to 8 mm. The length of the first section within this range can promote the recovery of semi-volatile substances; and / or,

[0017] The length of the second section is 15 to 35 mm. Within this range, the second section can adsorb VOCs and some compounds with higher boiling points in the gas; and / or,

[0018] The length of the third section is 10 to 30 mm. When the length of the third section is within this range, quantitative sampling and analysis of VVOC can be achieved.

[0019] In some embodiments, the volatile gas to be measured is desorbed and then separated, and the volatile organic compounds in the collection tube are enriched using a thermal desorption device in the separated volatile gas:

[0020] The desorption heating rate is 40-60°C / min; and / or,

[0021] The desorption temperature is 285-305°C; and / or,

[0022] The desorption time is 10 to 15 minutes; and / or,

[0023] The desorption gas flow rate is 50 to 78 mL / min; and / or,

[0024] The desorption cold trap temperature is -150°C to -130°C. Within this temperature range, the cold trap can retain small odor molecules in the gas, increasing the gas concentration at the olfactory port. This allows the odor evaluator to perceive a clearer odor, enabling accurate evaluation of odor intensity and properties. Furthermore, the detection limit of the test substance is lowered, and the detected odor substances are more comprehensive, which is more conducive to odor tracing analysis.

[0025] Control the desorption temperature, heating rate and desorption flow rate to give the adsorbed substances sufficient kinetic energy so that they can be desorbed with the flow of carrier gas, thereby increasing the detection content of volatile substances.

[0026] In some embodiments, in the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas:

[0027] Qualitative and quantitative detection methods include gas chromatography. Using gas chromatography for qualitative and quantitative detection can improve the reliability and accuracy of measurement.

[0028] In some embodiments, the gas chromatography column comprises a capillary chromatography column; and / or,

[0029] The flow rate of the gas chromatography column is 1-2 mL / min. Within this range, the gas chromatography column can achieve sufficient separation of compounds while maintaining good peak shape, without shortening the life of the column due to excessive flow rate or column pressure, or reducing work efficiency due to excessive flow rate; and / or,

[0030] The split ratio of the chromatographic column of the gas chromatography method is (8-12): 1. When the split ratio of the chromatographic column of the gas chromatography method is within this range, the compounds can be better separated, and the concentration of the compounds is easy for odorants to clearly identify and distinguish.

[0031] In some embodiments, the gas chromatography temperature program includes: an initial column temperature of 30-40°C, maintained for 0-1 minute, then increased at 3-4°C / min to 90-92°C, then increased at 5-6°C / min to 140-160°C, and finally increased at 10-12°C / min to 280-300°C, where it was maintained for 3-5 minutes. This temperature program achieves optimal separation, with sufficient separation of compounds and good peak shape for most substances. With optimal separation, analysis time is also minimized.

[0032] In some embodiments, the gas chromatography detection conditions include acquisition mode TIC+SIM, wherein:

[0033] Ion source temperature 220-240°C; and / or,

[0034] Quadrupole temperature 130-170°C; and / or

[0035] Scanning range: 30~500amu.

[0036] Under these detection conditions, the sample molecules can be better ionized, and the ions can be better screened and separated, ensuring accurate detection of the target analytes and the various ion fragments they may produce.

[0037] In some embodiments, in the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas:

[0038] The humidified auxiliary gas flow rate of the olfactometer is 5-7 mL / min; and / or,

[0039] The humidified gas of the olfactometer comprises water vapor; and / or,

[0040] The flow rate of the heated auxiliary gas of the olfactometer is 35-45 mL / min; and / or,

[0041] The heating assist gas for the olfactometer consists of nitrogen.

[0042] Under these olfactory test conditions, a suitable heating auxiliary gas flow rate can allow olfactory personnel to have enough time to perceive and distinguish the characteristics and intensity of the odor, and a certain amount of humidified auxiliary gas can help olfactory personnel better identify and evaluate the odor.

[0043] In some embodiments, in the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas:

[0044] The sniffing distance is 1 to 2 cm. The odor evaluator places his nose completely in the center of the odor port, about 1 to 2 cm away from the exit end of the capillary column, and maintains normal breathing. After smelling the odor, a quick evaluation of the intensity level and the description of the odor properties can improve the accuracy of the odor. The background odor can be evaluated first to ensure that the odor intensity is non-irritating. If the background odor does not meet the requirements, a blank test can be performed before the sample test until the background odor meets the requirements. The method for establishing the odor tracing model can be effectively applied to the odor analysis and tracing of complete vehicles, automobile interior parts (such as seats, roofs, trunk lids, carpets, door frame seals), and automobile interior materials (such as leather). BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0046] Figure 1 This is a flowchart of a method for establishing an odor tracing model according to an embodiment of the present application.

[0047] Figure 2 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method in Example 1 of the present application.

[0048] Figure 3 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method of Example 2 of the present application.

[0049] Figure 4 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method in Example 3 of the present application.

[0050] Figure 5 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method in Example 4 of the present application.

[0051] Figure 6 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method in Example 5 of the present application.

[0052] Figure 7 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method of Example 6 of the present application.

[0053] Figure 8 This is the mass spectrum of the gas sample used in the odor tracing model establishment method of Examples 7, 8, and 9 of the present application.

[0054] Figure 9 This is the mass spectrum and odor intensity correspondence diagram of the gas sample of the odor tracing model establishment method in Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0055] To make the objectives, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the embodiments described are part of the embodiments of this application, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of this application without making any creative efforts shall fall within the scope of protection of this application.

[0056] Driven by the need for lightweight vehicles, polymer materials are increasingly being used in automotive interiors. However, these polymers release volatile organic compounds (VOCs) when exposed to sunlight and high temperatures. Due to the prolonged closed state of vehicles, these compounds can ultimately lead to unpleasant odors within the vehicle. Odor perception is one of the most intuitive psychological experiences of the human body, and more and more people are beginning to consider in-car odor as a component of vehicle quality assessment. Therefore, for automakers, accurately identifying the source of odors and rectifying them is crucial for effectively improving vehicle odor quality assessment. Currently, odor evaluation of complete vehicles and their interiors is primarily based on sensory evaluation methods such as the vehicle cabin method, the parts bag method, the bottle method, and the three-point odor bag comparison method. However, in-car odor is a combination of multiple odorous substances, and subjective perception alone cannot distinguish or accurately trace odors.

[0057] For example, a method for tracing and controlling leather odor includes the following steps: sampling finished leather products: taking a predetermined length of leather sample and placing it directly into a glass sampling tube, inserting quartz wool at both ends of the tube, placing it in a specified orientation in the sample tray of a thermal desorber, and initiating gas chromatography-mass spectrometry olfaction analysis of odorous substances. By combining gas chromatography-mass spectrometry analysis with automated olfaction analysis of finished leather products and related raw materials, odorous substance identification and chromatographic-mass spectrometry spectrum correspondence analysis are performed, allowing significant odor contributors to be traced back to the leather materials added during the production process. This technical solution primarily utilizes pretreatment studies of the test substances to obtain consistent analytical data, which serves as valid data for subsequent odor analysis and control. In actual testing, sampling conditions, as well as subsequent thermal desorption, GC-MS, and olfactometer testing conditions, significantly influence test results. Furthermore, the diverse variety of automotive interior components and the complex sources of odors make comprehensive and accurate odor tracing analysis of the entire vehicle, its components, and its interior materials difficult.

[0058] In view of this, the present application provides a method for establishing an odor tracing model to solve the existing problem of being unable to distinguish and accurately trace odors.

[0059] First, as Figure 1 As shown, the present application provides a method for establishing an odor tracing model, comprising the following steps:

[0060] S100, using a collection tube to collect the volatile gas to be tested;

[0061] S200, desorbing and separating the volatile gas to be measured to obtain separated volatile gas;

[0062] S300, performing qualitative and quantitative detection and olfactory testing on the separated volatile gases simultaneously;

[0063] S400, associating the qualitative and quantitative test results with the olfactory identification test results to establish an odor tracing model;

[0064] The collecting tube includes a first section, a second section and a third section arranged in sequence. The adsorbent material of the first section includes quartz wool, the adsorbent material of the second section includes a high molecular linear polymer, and the adsorbent material of the third section includes graphitized carbon black.

[0065] In the present application, the capture tube includes a first section, a second section and a third section arranged in sequence. The material of the adsorbent in the first section includes quartz wool, the material of the adsorbent in the second section includes a high molecular linear polymer, and the material of the adsorbent in the third section includes graphitized carbon black. The quartz wool mainly promotes the recovery of semi-volatile substances (substances after C22). The high molecular linear polymer in the middle section is a weak adsorbent with the characteristics of high thermal stability, antioxidant, and low adsorption of water. The adsorption principle mainly relies on the intermolecular interaction between the π electrons in the molecules and the lone electron pairs on the ether oxygen atoms and the adsorbed substances; the high molecular linear polymer has good adsorption performance for most substances with medium and high boiling points (boiling point of 50-260°C, test conditions of 20°C, 0.1-4kPa), and is suitable for the enrichment of volatile organic compounds of C6 to C26, but has poor adsorption performance for small molecular substances with low boiling points. Back-end graphitized carbon black is a strong adsorbent that can be used for the adsorption and enrichment of C4-C20 volatile compounds. The enrichment mainly relies on the induction and dispersion effects of the plane of the graphite crystal on the adsorbed substances, and has a broad spectrum of adsorption properties. This application uses multi-stage adsorbents to adjust the adsorbent substances from the most retained to the least retained, effectively expanding the range of adsorbable volatiles, achieving adsorption of volatile substances from 1,3-butadiene to C30, increasing the adsorption range of target analytes, and improving the accuracy of analysis. After desorption, the enriched volatile organic compounds are subjected to qualitative and quantitative detection and olfactory testing, which can associate the sensory characteristics of the odor substances with their properties and content, and realize the establishment of an odor tracing model. The odor tracing model can be used to trace the source of unknown odors and quickly find the source of the odor. The odor intensity and properties obtained from the olfactory test are analyzed in correspondence with the qualitative and quantitative spectra, and the source of the odor substances in the vehicle can be traced back. Ultimately, by adjusting the material formula and production process, the odor is improved step by step from materials to parts to the entire vehicle, achieving the goal of targetedly solving the source of the odor in the vehicle.

[0066] It should be noted that, usually the first section is the front section of the collection tube in the collection direction, the second section is the middle section of the collection tube in the collection direction, and the third section is the last section of the collection tube in the collection direction. With this arrangement, the gas passes through the front section of the collection tube in turn, and the semi-volatile substances (substances after C22) in the gas are adsorbed by the quartz wool; then enters the middle section, and the volatile organic compounds of C6 to C26 in the gas are adsorbed by the high molecular linear polymer; then enters the last section, and the small molecular substances in the gas are adsorbed by graphitized carbon black, thereby effectively expanding the range of adsorbable volatile substances and realizing the adsorption of volatile substances from 1,3-butadiene to C30.

[0067] In conjunction with the first aspect, in some embodiments provided herein, the high molecular weight linear polymer includes at least one of Tenax GC, Tenax TA, and Tenax GR. Using at least one of these high molecular weight linear polymers can improve the enrichment of C6-C26 volatile organic compounds. Tenax GC is poly-2,6-diphenyl-p-phenylene ether, Tenax TA is 2,6-diphenylfuran, and Tenax GR is composed of 70% Tenax TA and 30% graphitized carbon black.

[0068] In conjunction with the first aspect, in some embodiments provided herein, the graphitized carbon black comprises at least one of Carbograph 5TD, Carbopack X, Carbopack B, Carbotrap, and ENVICarb SPE. Using at least one of these graphitized carbon blacks can improve the adsorption and enrichment of C4-C20 volatile compounds. Carbograph 5TD is primarily composed of graphitized carbon. Carbopack X is a black carbon-based adsorbent. Carbopack B is a black fine-particle carbon adsorbent. Carbotrap is a carbon-based adsorbent. ENVICarb SPE is a solid phase extraction (SPE) carbon adsorbent.

[0069] In combination with the first aspect, in some embodiments provided in the present application, the particle size of the adsorbent material of the second section is 0.18 mm to 0.25 mm. The particle size of the adsorbent material of the second section is within this range, which can further improve the enrichment of volatile organic compounds of C6 to C26.

[0070] In combination with the first aspect, in some embodiments provided in the present application, the particle size of the adsorbent material of the third section is 0.42 mm to 0.64 mm. The particle size of the adsorbent material of the third section is within this range, which can further improve the enrichment of volatile organic compounds of C4 to C20.

[0071] In combination with the first aspect, in some embodiments provided in the present application, the length of the first segment is 3 to 8 mm. When the length of the first segment is within this range, the recovery of semi-volatile substances can be promoted.

[0072] In combination with the first aspect, in some embodiments provided in the present application, the length of the second segment is 15 to 35 mm. When the length of the second segment is within this range, VOCs and some compounds with higher boiling points in the gas can be adsorbed.

[0073] In combination with the first aspect, in some embodiments provided in the present application, the length of the third segment is 10 to 30 mm. When the length of the third segment is within this range, quantitative sampling and analysis of VVOC can be achieved.

[0074] In combination with the first aspect, in some embodiments provided in the present application, the volatile gas to be tested is desorbed and then separated, and the volatile organic matter in the capture tube is enriched in the separated volatile gas using a thermal desorption device: the desorption heating rate is 40 to 60°C / min.

[0075] In combination with the first aspect, in some embodiments provided in the present application, the volatile gas to be tested is desorbed and then separated, and the volatile organic compounds in the collection tube are enriched using a thermal desorption device in the separated volatile gas: the desorption temperature is 285-305°C.

[0076] In combination with the first aspect, in some embodiments provided in the present application, the volatile gas to be tested is desorbed and then separated, and the volatile organic compounds in the collection tube are enriched using a thermal desorption device in the separated volatile gas: the desorption time is 10 to 15 minutes.

[0077] In combination with the first aspect, in some embodiments provided in the present application, the volatile gas to be tested is desorbed and then separated, and the volatile organic matter in the capture tube is enriched using a thermal desorption device in the separated volatile gas: the desorption gas flow rate is 50 to 78 mL / min.

[0078] In conjunction with the first aspect, in some embodiments provided herein, the volatile gas to be tested is desorbed and separated, and the volatile organic compounds in the separated volatile gas are enriched in a capture tube using a thermal desorption device. The desorption cold trap temperature is -150°C to -130°C. Within this cold trap temperature range, small odor molecules in the gas are retained, increasing the gas concentration at the olfactory port. This makes the odor perceived by the odor evaluator clearer, enabling accurate evaluation of the odor intensity level and odor properties. Furthermore, the detection limit of the test substance is reduced, and the detected odor substances are more comprehensive, which is more conducive to odor tracing analysis.

[0079] Control the desorption temperature, heating rate and desorption flow rate to give the adsorbed substances sufficient kinetic energy so that they can be desorbed with the flow of carrier gas, thereby increasing the detection content of volatile substances.

[0080] In conjunction with the first aspect, in some embodiments provided herein, in the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gases, the qualitative and quantitative detection methods include gas chromatography. Using gas chromatography for qualitative and quantitative detection can improve measurement reliability and accuracy.

[0081] In combination with the first aspect, in some embodiments provided in the present application, the chromatographic column of the gas chromatography method includes a capillary chromatographic column.

[0082] In combination with the first aspect, in some embodiments provided in the present application, the flow rate of the chromatographic column of the gas chromatography method is 1 to 2 mL / min. The flow rate of the chromatographic column of the gas chromatography method is within this range, which can ensure sufficient separation of the compounds and maintain a good peak shape. The life of the chromatographic column will not be shortened due to excessive flow rate or excessive column pressure, nor will the work efficiency be reduced due to too low flow rate.

[0083] In conjunction with the first aspect, in some embodiments provided herein, the split ratio of the gas chromatography column is (8-12): 1. Within this range, the split ratio of the gas chromatography column can better separate the compounds, and the concentration of the compounds is easy for the odorist to clearly identify and distinguish.

[0084] In conjunction with the first aspect, in some embodiments provided herein, the temperature program of the gas chromatography method includes: maintaining the initial column temperature at 30-40°C for 0-1 min, heating to 90-92°C at 3-4°C / min, heating to 140-160°C at 5-6°C / min, heating to 280-300°C at 10-12°C / min, and maintaining for 3-5 min. Under this temperature program, the optimal separation effect can be obtained, the compounds have sufficient separation, and most substances can obtain good peak shapes. Under the optimal separation effect, the analysis time is also the shortest.

[0085] In combination with the first aspect, in some embodiments provided in the present application, the detection conditions of the gas chromatography include an acquisition mode TIC+SIM, wherein: the ion source temperature is 220-240°C.

[0086] In combination with the first aspect, in some embodiments provided in the present application, the detection conditions of the gas chromatography include an acquisition mode TIC+SIM, wherein: the quadrupole temperature is 130-170°C.

[0087] In combination with the first aspect, in some embodiments provided in the present application, the detection conditions of the gas chromatography include an acquisition mode TIC+SIM, wherein: the scanning range is 30 to 500 amu.

[0088] Under these detection conditions, the sample molecules can be better ionized, and the ions can be better screened and separated, ensuring accurate detection of the target analytes and the various ion fragments they may produce.

[0089] In combination with the first aspect, in some embodiments provided in the present application, the separated volatile gas is subjected to qualitative and quantitative detection and olfactory testing simultaneously: the humidification auxiliary gas flow rate of the olfactometer is 5 to 7 mL / min.

[0090] In combination with the first aspect, in some embodiments provided in the present application, the separated volatile gas is subjected to qualitative and quantitative detection and olfactory testing simultaneously: the humidified gas of the olfactometer includes water vapor.

[0091] In combination with the first aspect, in some embodiments provided in the present application, the separated volatile gas is subjected to qualitative and quantitative detection and olfactory testing simultaneously: the flow rate of the heating auxiliary gas of the olfactometer is 35-45 mL / min.

[0092] In combination with the first aspect, in some embodiments provided in the present application, in the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas, the heating auxiliary gas of the olfactometer includes nitrogen.

[0093] Under these olfactory test conditions, a suitable heating auxiliary gas flow rate can allow olfactory personnel to have enough time to perceive and distinguish the characteristics and intensity of the odor, and a certain amount of humidified auxiliary gas can help olfactory personnel better identify and evaluate the odor.

[0094] In combination with the first aspect, in some embodiments provided in the present application, in the qualitative and quantitative detection and olfactory identification test of the separated volatile gases, the olfactory identification distance is 1 to 2 cm. The odor evaluator places his nose completely in the center of the olfactory identification port, about 1 to 2 cm away from the outlet of the capillary column, and maintains normal breathing. After smelling the odor, a quick evaluation of the intensity level and the description of the odor properties can improve the accuracy of the olfactory identification. The background odor can be evaluated first to ensure that the odor intensity is non-irritating. If the background odor does not meet the requirements, a blank test can be performed before the sample test until the background odor meets the requirements. The method for establishing an odor tracing model can be effectively applied to odor analysis and tracing in complete vehicles, automobile interior parts (such as seats, roofs, trunk lids, carpets, door frame seals), and automobile interior materials (such as leather).

[0095] The odor intensity levels can be divided into:

[0096] Level 1: Can perceive but cannot distinguish the type of odor;

[0097] Level 2: Can perceive odors and distinguish odor types;

[0098] Level 3: The smell is irritating;

[0099] Level 4: The smell is very irritating (unbearable).

[0100] The present application will be described below with reference to specific embodiments.

[0101] Example 1

[0102] A method for establishing an odor tracing model comprises the following steps:

[0103] A gas sample from a certain vehicle model was enriched using a sample capture tube; the sample capture tube was loaded with multiple sections of adsorbent stainless steel tubes. The sample capture tube had an inner diameter of 5 mm, with a 5 mm long front section loaded with quartz wool, a 35 mm long middle section loaded with Tenax TA, and a 20 mm long rear section loaded with graphitized carbon black Carbograph 5TD.

[0104] The enriched gas is subjected to secondary desorption by a thermal desorption device and then injected into a gas chromatograph (GC) for separation; wherein the starting temperature of the thermal desorption device is 40°C, the desorption heating rate is 60°C / min, the desorption temperature is 300°C, the desorption time is 10 min, the desorption gas flow rate is 78 mL / min, the cold trap temperature is -150°C, the desorption gas is helium, the cold trap desorption temperature is 300°C, and the cold trap desorption time is 5 min;

[0105] GC separation conditions were as follows: capillary column, HP-5MS, dimensions 60 m × 0.25 mm × 0.25 μm; gradient temperature program: initial column temperature 40°C, temperature increased at 3°C / min to 92°C, temperature increased at 5°C / min to 160°C, temperature increased at 10°C / min to 280°C, and held for 5 min; column flow rate 1.6 mL / min, split ratio 8:1;

[0106] The separated gas is split into two streams by a diverter valve at a volume ratio of 1:1. One stream enters the mass spectrometer (MS) for qualitative and quantitative analysis of the sample, while the other stream enters the olfaction port of the odor analyzer, where an odor evaluator evaluates the odor intensity level and odor properties.

[0107] Among them, the MS detection conditions were: acquisition mode: TIC+SIM, ion source temperature of 230°C, quadrupole temperature of 150°C, and scanning range of 30-500 amu;

[0108] The heating auxiliary gas of the olfactometer is nitrogen, and the heating auxiliary gas flow rate is 40mL / min; the humidification gas is water vapor, and the humidification gas flow rate is 6mL / min;

[0109] The odor intensity, odor properties, and qualitative results, quantitative results, and retention time of GC-MS output were integrated to establish an odor traceability model, as shown in Table 1. The odor profile and odor profile are shown in Table 1. Figure 2 As shown, it should be noted that the blue line is the odor identification map, the black line is the mass spectrum map, and the other figures are the same.

[0110] Table 1 Results of the method for establishing the odor tracing model in Example 1

[0111]

[0112]

[0113] “ / ” means that the odor evaluator did not smell the odor substance.

[0114] Example 2

[0115] A method for establishing an odor tracing model comprises the following steps:

[0116] A sample capture tube was used to collect gas samples emitted from a vehicle pillar assembly within a sampling bag. The sample capture tube consisted of multiple sections of adsorbent stainless steel tubes. The tube had an inner diameter of 5 mm, with a front section (3 mm long) filled with quartz wool, a middle section (25 mm long) filled with Tenax TA, and a rear section (30 mm long) filled with graphitized carbon black, Carbograph 5TD.

[0117] The enriched gas is subjected to secondary desorption by a thermal desorption device and then injected into a gas chromatograph (GC) for separation; wherein the starting temperature of the thermal desorption device is 40°C, the desorption heating rate is 40°C / min, the desorption temperature is 285°C, the desorption time is 5 min, the desorption gas flow rate is 50 mL / min, the cold trap temperature is -140°C, the desorption gas is helium, the cold trap desorption temperature is 285°C, and the cold trap desorption time is 5 min;

[0118] GC separation conditions were as follows: capillary column, HP-5MS, dimensions 60 m × 0.25 mm × 0.25 μm; gradient temperature program: initial column temperature 40°C, temperature increased at 3°C / min to 92°C, temperature increased at 5°C / min to 160°C, temperature increased at 10°C / min to 280°C, and held for 5 min; column flow rate 1.6 mL / min, split ratio 12:1;

[0119] The separated gas is split into two streams by a diverter valve at a volume ratio of 1:1. One stream enters the mass spectrometer (MS) for qualitative and quantitative analysis of the sample, while the other stream enters the olfaction port of the odor analyzer, where an odor evaluator evaluates the odor intensity level and odor properties.

[0120] Among them, the MS detection conditions were: acquisition mode: TIC+SIM, ion source temperature of 220°C, quadrupole temperature of 130°C, and scanning range of 30-500 amu;

[0121] The heating auxiliary gas of the olfactometer is helium, and the heating auxiliary gas flow rate is 35mL / min; the humidification gas is water vapor, and the humidification gas flow rate is 5mL / min;

[0122] The odor intensity, odor properties, and qualitative results, quantitative results, and retention time of GC-MS output were integrated to establish an odor traceability model, as shown in Table 2. The odor profile and odor profile are shown in Table 2. Figure 3shown.

[0123] Table 2 Results of the method for establishing the odor tracing model in Example 2

[0124]

[0125]

[0126] “ / ” means that the odor evaluator did not smell the odor substance.

[0127] Example 3

[0128] A method for establishing an odor tracing model comprises the following steps:

[0129] A sample capture tube was used to collect gas samples emitted from a certain vehicle roof assembly within a sampling bag. The sample capture tube consisted of three sections of adsorbent stainless steel tubes with an inner diameter of 5 mm. The front section (8 mm long) was filled with quartz wool, the middle section (15 mm long) was filled with Tenax TA, and the rear section (30 mm long) was filled with graphitized carbon black Carbograph 5TD.

[0130] The enriched gas is subjected to secondary desorption by a thermal desorption device and then injected into a gas chromatograph (GC) for separation; wherein the starting temperature of the thermal desorption device is 40°C, the desorption heating rate is 50°C / min, the desorption temperature is 305°C, the desorption time is 10 min, the desorption gas flow rate is 60 mL / min, the cold trap temperature is -130°C, the desorption gas is helium, the cold trap desorption temperature is 305°C, and the cold trap desorption time is 5 min;

[0131] GC separation conditions were as follows: capillary column, HP-5MS, dimensions 60 m × 0.25 mm × 0.25 μm; gradient temperature program: initial column temperature 40°C, temperature increased at 3°C / min to 92°C, temperature increased at 5°C / min to 160°C, temperature increased at 10°C / min to 280°C, and held for 5 min; column flow rate 1.6 mL / min, split ratio 10:1;

[0132] The separated gas is split into two streams by a diverter valve at a volume ratio of 1:1. One stream enters the mass spectrometer (MS) for qualitative and quantitative analysis of the sample, while the other stream enters the olfaction port of the odor analyzer, where an odor evaluator evaluates the odor intensity level and odor properties.

[0133] Among them, the MS detection conditions were: acquisition mode: TIC+SIM, ion source temperature of 240°C, quadrupole temperature of 170°C, and scanning range of 30-500 amu;

[0134] The heating auxiliary gas of the olfactometer is nitrogen, and the heating auxiliary gas flow rate is 45mL / min; the humidification gas is water vapor, and the humidification gas flow rate is 7mL / min;

[0135] Integrate the odor intensity, odor properties, and the qualitative results, quantitative results, and retention time output by GC-MS to establish an odor traceability model, as shown in Table 3. The odor spectrum and odor spectrum are as follows: Figure 4 shown.

[0136] Table 3 Results of the method for establishing the odor tracing model in Example 3

[0137]

[0138] “ / ” means that the odor evaluator did not smell the odor substance.

[0139] Example 4

[0140] A method for establishing an odor source tracing model is similar to Example 2, except that the cold trap temperature is -30°C, the gas atmosphere spectrum and the odor spectrum are as follows: Figure 5 shown.

[0141] Compared with the cold trap temperature of -150℃, the intensity of the smell detected will be smaller and more vague when the cold trap temperature is -30℃. It also reduces the detection limit of the substance to be tested, and the number of detected substances will be reduced.

[0142] Example 5

[0143] A method for establishing an odor source tracing model is similar to Example 3, except that the split ratio is 50:1, the temperament spectrum and the odor spectrum are as follows: Figure 6 shown.

[0144] When the split ratio is 50:1, the gas concentration entering the olfactory port of the odor analyzer is low, and the odor evaluator has certain difficulties in accurately evaluating the odor intensity level and odor properties.

[0145] In Example 3, the split ratio is 10:1, the separation degree of the test substances is good, and the odor concentration is conducive to the odor evaluator to easily identify the odor nature and evaluate the odor intensity, thereby improving the accuracy of olfactory identification.

[0146] Example 6

[0147] A method for establishing an odor tracing model is similar to Example 3, except that the split ratio is 5:1, the temperament spectrum and the odor spectrum are as follows: Figure 7 As shown, Figure 7 (Top) is the temperament map, Figure 7(Bottom) shows the olfactory spectrum. At a split ratio of 5:1, the inlet gas concentration is high, reducing the separation of the analytes in the chromatographic column. This makes it difficult for odor assessors to accurately and efficiently distinguish the different odorants in the sample.

[0148] Example 7

[0149] A method for establishing an odor tracing model is similar to Example 3, except that: the leather types are different, and the gradient heating program is: the initial column temperature is 50°C, maintained for 1 minute, heated to 92°C at 5°C / min, heated to 160°C at 10°C / min, and heated to 300°C at 20°C / min and maintained for 8 minutes. There is a lot of overlap in the peaks of the substances to be tested, which has a certain impact on the accuracy of analysis and olfactory identification.

[0150] Example 8

[0151] A method for establishing an odor tracing model is similar to Example 3, except that: the leather types are different, and the gradient heating program is: the initial column temperature is maintained at 40°C for 2 minutes, the temperature is increased at 3°C / min to 92°C, the temperature is increased at 5°C / min to 160°C, and the temperature is increased at 10°C / min to 280°C and maintained for 10 minutes. The analysis and olfactory time is longer, and the peak cannot be completely generated, which has a certain impact on the accuracy of the detection.

[0152] Example 9

[0153] A method for establishing an odor tracing model is similar to Example 3, except that: the leather types are different, and the gradient heating program is: the initial column temperature is 40°C, the temperature is increased to 92°C at 3°C / min, the temperature is increased to 160°C at 5°C / min, and the temperature is increased to 280°C at 10°C / min, and maintained for 5 minutes. This improves the separation of the substances to be tested and shortens the analysis time of the substances to be tested, thereby improving the precision and accuracy of the test method.

[0154] The gas chromatography-mass spectra of Examples 7-9 are as follows: Figure 8 As shown, Figure 8 (Top) is the mass spectrum of Example 7, Figure 8 (Middle) is the mass spectrum of Example 8, Figure 8 (Bottom) is the mass spectrum of Example 9.

[0155] Comparative Example 1

[0156] A method for establishing an odor tracing model is the same as Example 2, except that the adsorbent in the three sections of the capture tube is Tenax TA, which narrows the adsorption range of volatile substances. In particular, some small molecular odor substances may not be captured, resulting in fewer types of odor substances detected in Comparative Example 1. Therefore, it is impossible to fully and effectively evaluate the odor of the sample gas. Its mass spectrum is shown in the figure below. Figure 9shown.

[0157] Comparative Example 2

[0158] A method for establishing an odor tracing model is similar to Example 2, except that the adsorbent in all three sections of the capture tube is graphitized carbon black Carbograph 5TD. In Comparative Example 2, Carbograph 5TD has good adsorption of VVOCs but poor adsorption of semi-volatile substances, and therefore cannot comprehensively and effectively evaluate the odor of the sample gas.

[0159] The terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not limited to the listed steps or units, but optionally includes steps or units that are not listed, or optionally includes other steps or units inherent to these processes, methods, products or devices. The terms "first", "second" and "third" are used to distinguish different objects, etc., and do not represent a sequence, nor do they limit the "first", "second" and "third" to different types.

[0160] In the description of the embodiments of this application, the words "exemplary," "for example," or "for example" are used to indicate examples, illustrations, or descriptions. Any embodiment or design described as "exemplary," "for example," or "for example" in the embodiments of this application should not be construed as being preferred or advantageous over other embodiments or designs. Rather, the use of words such as "exemplary," "for example," or "for example" is intended to present the relevant concepts in a concrete manner.

[0161] In the description of the embodiments of the present application, unless otherwise specified, “ / ” means or, for example, A / B can mean A or B; “and / or” in the text is merely a description of the association relationship of associated objects, indicating that three relationships may exist, for example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. In addition, in the description of the embodiments of the present application, “multiple” refers to two or more than two.

[0162] In some processes described in the embodiments of the present application, multiple operations or steps are included that appear in a specific order. However, it should be understood that these operations or steps may not be performed in the order in which they appear in the embodiments of the present application or may be performed in parallel. The sequence numbers of the operations are only used to distinguish between different operations, and the sequence numbers themselves do not represent any order of execution. In addition, these processes may include more or fewer operations, and these operations or steps may be performed in sequence or in parallel, and these operations or steps may be combined.

[0163] The above are only preferred embodiments of the present application and do not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for establishing an odor tracing model, characterized in that: The following steps are involved: Use a capture tube to collect the volatile gas to be tested; Desorbing and separating the volatile gas to be measured to obtain the separated volatile gas; The separated volatile gases are subjected to qualitative and quantitative detection and olfactory testing simultaneously; Correlate the qualitative and quantitative test results with the olfactory identification test results to establish an odor tracing model; The collecting tube includes a first section, a second section and a third section arranged in sequence. The adsorbent material of the first section includes quartz wool, the adsorbent material of the second section includes a high molecular linear polymer, and the adsorbent material of the third section includes graphitized carbon black.

2. The method for establishing an odor source tracing model according to claim 1, wherein: The high molecular linear polymer includes at least one of Tenax GC, Tenax TA and Tenax GR; and / or, The graphitized carbon black includes at least one of Carbograph 5TD, Carbopack X, Carbopack B, Carbotrap, and ENVICarb SPE.

3. The method for establishing an odor source tracing model according to claim 1, wherein: The particle size of the adsorbent material of the second stage is 0.18 mm to 0.25 mm; and / or, The particle size of the adsorbent material in the third section is 0.42 mm to 0.64 mm; and / or, The length of the first segment is 3 to 8 mm; and / or, The length of the second segment is 15 to 35 mm; and / or, The length of the third section is 10 to 30 mm.

4. The method for establishing an odor source tracing model according to claim 1, wherein: The volatile gas to be measured is desorbed and then separated to obtain the following volatile gas: The desorption heating rate is 40-60°C / min; and / or, The desorption temperature is 285-305°C; and / or, The desorption time is 10 to 15 minutes; and / or, The desorption gas flow rate is 50 to 78 mL / min; and / or, The desorption cold trap temperature is -150℃~-130℃.

5. The method for establishing an odor source tracing model according to claim 1, wherein: In the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas: Qualitative and quantitative detection methods include gas chromatography.

6. The method for establishing an odor source tracing model according to claim 5, wherein: The chromatographic column of the gas chromatography method comprises a capillary chromatographic column; and / or, The flow rate of the gas chromatography column is 1 to 2 mL / min; and / or, The split ratio of the chromatographic column of the gas chromatography method is (8-12):

1.

7. The method for establishing an odor source tracing model according to claim 5, wherein: The temperature rising program of the gas chromatography method includes: maintaining the initial column temperature at 30-40°C for 0-1 minute, heating to 90-92°C at 3-4°C / min, heating to 140-160°C at 5-6°C / min, heating to 280-300°C at 10-12°C / min, and maintaining for 3-5 minutes.

8. The method for establishing an odor source tracing model according to claim 5, wherein: The detection conditions of the gas chromatography include: Ion source temperature 220-240°C; and / or, Quadrupole temperature 130-170°C; and / or Scanning range: 30~500amu.

9. The method for establishing an odor source tracing model according to claim 1, wherein: In the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas: The humidified auxiliary gas flow rate of the olfactometer is 5-7 mL / min; and / or, The humidified gas of the olfactometer comprises water vapor; and / or, The flow rate of the heated auxiliary gas of the olfactometer is 35-45 mL / min; and / or, The heating assist gas for the olfactometer consists of nitrogen.

10. The method for establishing an odor source tracing model according to claim 1, wherein: In the simultaneous qualitative and quantitative detection and olfactory testing of the separated volatile gas: The smelling distance is 1 to 2 cm.

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