Volatile aldehyde ketone compound fingerprint as well as construction method and application thereof

Abstract

The invention relates to the technical field of volatile organic compounds (VOCs) analysis, in particular to a volatile aldehyde ketone compound fingerprint spectrum and a construction method and application thereof. Comprising the following steps: (1) respectively preparing a sample to-be-tested solution and a standard solution, and carrying out ultra-high performance liquid chromatography-ultraviolet detection to obtain chromatographic information of the sample to-be-tested solution and chromatographic information of the standard solution; (2) taking the chromatographic information of the standard solution as a reference, affiliating the chromatographic information of the sample to-be-tested solution, and performing similarity calculation on the chromatographic information of the sample to-be-tested solution to obtain a volatile aldehyde ketone compound fingerprint spectrum; the aldehyde ketone compounds are selected from at least eight of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, butenal, methylacrolein, 2-butanone, n-butyraldehyde, benzaldehyde, valeraldehyde, m-tolualdehyde and acetaldehyde. The method is rapid, simple, good in precision and high in repeatability.

Description

Technical Field

[0001] The present invention relates to the technical field of volatile organic compound (VOCs) analysis, and in particular to a fingerprint spectrum of volatile aldehyde and ketone compounds, a construction method thereof and an application thereof. Background Art

[0002] Volatile Organic Compounds (VOCs) are generally organic compounds with a saturated vapor pressure greater than 133.3 Pa at room temperature, or a boiling point below 260°C at normal pressure. They mainly include three categories: aliphatic hydrocarbons, aromatic hydrocarbons and polar organic compounds.

[0003] Aldehydes and ketones are an important class of volatile organic compounds (VOCs) in the atmosphere. They are not only important components of photochemical smog, but also important precursors of photochemical smog formation. In addition, aldehydes and ketones are also important sources of HOx free radicals in the atmosphere, which contribute to the formation of secondary organic aerosols in the atmosphere and have a direct negative impact on human health.

[0004] Its molecular structure contains a common functional group - carbonyl, which is an important component of polar volatile organic compounds; the sources of aldehydes and ketones in the atmosphere are relatively complex, mainly from industrial activities, automobile exhaust, fossil combustion and biomass combustion, plant emissions and other primary sources, as well as secondary sources of photochemical oxidation of organic matter. The types and quantities of aldehydes and ketones emitted by different emission sources are quite different, and have their own characteristics.

[0005] At present, oilfield processing stations are the main source of volatile organic compound emissions in oilfields. There are many studies on their VOCs emissions, mainly focusing on the detection of VOCs composition and concentration at the plant boundary; some ultra-heavy oil processing stations are close to residential areas (biomass combustion, plant emissions) or other emission sources, and various VOCs emission sources are mixed with each other. It is necessary to identify and determine whether the pollution is caused by volatile organic compound emissions from the processing stations.

[0006] Chinese invention patent application CN111983115A discloses a method for detecting VOCs in air, which includes determining the location of a sampling point, collecting air samples, and using a pump to pass the air samples through an adsorbent to collect VOCs; enriching the collected VOCs through a VOCs adsorption treatment device in air; analyzing the components and concentrations of VOCs in the air using GC-FID / MS coupling technology for the enriched VOCs samples; analyzing the formaldehyde content in indoor air using acetylacetone spectrophotometry; preparing standard sample solutions of multiple volatile compounds and drawing standard curves, and analyzing the enriched VOCs samples to obtain corresponding test results. This method does not involve UPLC detection.

[0007] Chinese invention patent application CN111983116A discloses a method for detecting pollution characteristics of VOCs in air based on GC-FID / MS, including: selecting an air detection area, and collecting and sampling air in the detection area; enriching VOCs in the collected air sample; using the heart cutting method to cut the light hydrocarbons in the enriched sample to the Plot column for analysis in the FID detector; separating the remaining components in the polysiloxane column, and analyzing them using the MS detector; and obtaining the detection results of VOCs in the air. The present invention can quickly detect air, improve the working efficiency of detection, and can accurately detect a variety of pollutants, but the method uses GC-FID / MS detection, which is relatively complicated.

[0008] Ultra Performance Liquid Chromatography (UPLC), with the help of the theories and principles of HPLC, covers new technologies such as small particle fillers, low system volume and rapid detection methods, increases the analysis throughput and chromatographic peak capacity, and has the characteristics of simplicity, accuracy, high sensitivity, good repeatability, and a wide range of detectors. It is one of the important methods for constructing fingerprint maps.

[0009] At present, there are no patent disclosures or literature reports on the use of UPLC method to conduct fingerprint studies on volatile organic compounds. Summary of the invention

[0010] In order to solve the above problems, the present invention provides a volatile aldehyde and ketone compound fingerprint spectrum and its construction method and application. The method performs similarity calculation on the VOCs of the super-heavy oil processing station, establishes a VOCs aldehyde and ketone UPLC fingerprint spectrum based on common peaks, and reflects the difference between the unknown sample and the control fingerprint spectrum from multiple angles of composition, distribution and content of 10 aldehyde and ketone substances, which is conducive to improving the accuracy of identification and judgment.

[0011] In order to achieve the above-mentioned invention object, the present invention provides the following technical solutions:

[0012] A method for constructing a fingerprint spectrum of volatile aldehyde and ketone compounds, characterized by comprising the following steps:

[0013] (1) preparing a sample test solution and a standard solution respectively, and performing ultra-high performance liquid chromatography-ultraviolet detection to obtain chromatographic information of the sample test solution and chromatographic information of the standard solution;

[0014] (2) Using the chromatographic information of the standard solution as a reference, the chromatographic information of the sample solution is attributed, and the similarity of the chromatographic information of the sample solution is calculated to obtain a fingerprint of volatile aldehyde and ketone compounds;

[0015] The aldehyde and ketone compounds are selected from at least eight of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, methacrolein, 2-butanone, n-butyraldehyde, benzaldehyde, valeraldehyde, m-methylbenzaldehyde and acetaldehyde.

[0016] Further preferably, the aldehyde and ketone compounds include formaldehyde, acetaldehyde, acetone, acrolein, 2-butanone, methacrolein, benzaldehyde, valeraldehyde, propionaldehyde and m-methylbenzaldehyde.

[0017] Preferably, the preparation of the sample test solution in step (1) comprises: sampling using an atmospheric sampler, eluting and collecting, and then filtering with a filter membrane.

[0018] Further preferably, the atmospheric sampler is a dual-gas-path constant-flow atmospheric sampler; the sampling flow rate is 580-620 mL / min, and the sampling time is 98-100 min.

[0019] Preferably, the elution solvent is acetonitrile; and the filter membrane is a 0.20-0.24 μm microporous filter membrane.

[0020] Preferably, the preparation of the standard solution in step (1) comprises: diluting a solution of a 2,4-dinitrophenylhydrazone derivative of an aldehyde or ketone compound to obtain the standard solution.

[0021] Further preferably, the reagent used for the dilution is acetonitrile; the concentration of the diluted standard solution is 1.8-2.2 mg / L.

[0022] Further preferably, the reagent used for the dilution is acetonitrile; the concentration of the standard solution is 1.8-2.2 mg / L, preferably 2.0 mg / L.

[0023] Preferably, the conditions for ultra-high performance liquid chromatography-ultraviolet detection in step (1) are: reverse phase alkyl chromatographic column, mobile phase A is water, mobile phase B is acetonitrile, gradient elution; detection wavelength is 350-370nm; column temperature is 30-40°C; injection volume is 18-22μL, flow rate is 0.2-0.4mL / min.

[0024] Further preferably, the conditions for elution with gradient changes in flow rate and mobile phase content are:

[0025] 0min, mobile phase A: 55%-65%; mobile phase B: 35%-45%;

[0026] 20min, mobile phase A: 35%-45%; mobile phase B: 55%-65%;

[0027] 30 min, mobile phase A: 0%-5%; mobile phase B: 95%-100%;

[0028] 32min, mobile phase A: 55%-65%; mobile phase B: 35%-45%;

[0029] 40min, mobile phase A: 58%-62%; mobile phase B: 38-42%;

[0030] Preferably, 0 min, mobile phase A: 60%; mobile phase B: 40%; 20 min, mobile phase A: 40%; mobile phase B: 60%; 30 min, mobile phase A: 0%; mobile phase B: 100%; 32 min, mobile phase A: 60%; mobile phase B: 40%; 40 min, mobile phase A: 60%; mobile phase B: 40%.

[0031] Further preferably, the reverse phase alkyl chromatography column is RP C8 1.7um 2.1×150mm Column.

[0032] Preferably, the reference standard for similarity calculation in step (2) is the "Chinese Medicine Chromatographic Fingerprint Similarity Evaluation System" published by the Chinese Pharmacopoeia Commission.

[0033] The present invention also relates to a fingerprint spectrum constructed by the above preparation method, wherein the ratio of the peak area of ​​each fingerprint peak to the total peak area in the fingerprint spectrum is greater than 0.5%.

[0034] The present invention also relates to a fingerprint spectrum constructed by the above construction method or the application of the above fingerprint spectrum in determining whether the volatile organic compound pollution source comes from an ultra-heavy oil processing station.

[0035] Preferably, the application process comprises the following steps:

[0036] (1) Sampling volatile organic compounds of unknown origin and preparing sample test solutions;

[0037] (2) Ultra-high performance liquid chromatography-ultraviolet detection to obtain chromatographic information of volatile aldehydes and ketones of unknown origin;

[0038] (3) Using the fingerprint of volatile aldehydes and ketones as a benchmark, the chromatographic information of volatile aldehydes and ketones of unknown origin is compared and determined.

[0039] Preferably, the judgment standard in step (3) is: if the chromatographic information of volatile aldehydes and ketones of the unknown sample is consistent with the reference fingerprint of volatile aldehydes and ketones, it can be determined that the source of contamination of the unknown sample comes from the super-heavy oil processing station; otherwise, it can be determined that the source of contamination of the unknown sample does not come from the super-heavy oil processing station.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) The present invention can accurately identify the difference between volatile organic compound emissions from super-heavy oil processing stations and other emission sources, and has the characteristics of being fast, simple, precise and highly repeatable;

[0042] (2) The present invention calculates the similarity of VOCs in the super-heavy oil processing station and establishes a VOCs aldehyde and ketone UPLC fingerprint based on common peaks, which reflects the differences between the unknown sample and the control fingerprint from multiple angles of composition, distribution and content of 10 aldehyde and ketone substances, which is conducive to improving the accuracy of identification and judgment;

[0043] (3) The VOCs aldehydes and ketones UPLC reference fingerprint of the super heavy oil processing station established by the present invention has a large number of reference peaks, which can more accurately and conveniently determine whether the unknown pollution comes from the super heavy oil processing station. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 is an overlapping chromatogram of aldehyde and ketone compounds of 10 samples in Example 1;

[0045] Figure 2 is the reference fingerprint of 10 aldehyde and ketone compounds in Example 1;

[0046] Figure 3 It is the VOCs aldehyde and ketone chromatogram information diagram of the unknown sample 1 in Example 4;

[0047] Figure 4 It is a comparison diagram of the fingerprint spectrum of unknown sample 1 and the control fingerprint spectrum in Example 4;

[0048] Figure 5 This is the VOCs aldehyde and ketone chromatogram information diagram of the unknown sample 2 in Example 5. DETAILED DESCRIPTION

[0049] The technical solutions in the embodiments of the present invention are further clearly described. The described embodiments are only a part of the present invention and are used to explain the present invention but not to limit the present invention. Therefore, other embodiments obtained by other technicians in the field without creative work all belong to the protection scope of the present invention.

[0050] The raw materials used in the embodiments of the present invention are all industrial products and are commercially available.

[0051] Example 1

[0052] 1. Construction of reference fingerprints of aldehyde and ketone compounds

[0053] (1) Preparation of sample test solution: 10 batches of VOCs samples from the super-heavy oil treatment station were continuously taken using a dual-gas constant-flow atmospheric sampler with a sampling flow rate of 600 mL / min and a sampling time of 99 min. The sample was connected to an ozone interference column and a sampling tube to automatically complete the sampling. The sampling tube was eluted and collected with 5 mL of acetonitrile and filtered with a 0.22 μm microporous filter membrane to obtain the sample test solution.

[0054] (2) Preparation of standard solutions: The standard solutions of 2,4-dinitrophenylhydrazone derivatives of 10 aldehydes and ketones, including formaldehyde, acetaldehyde, acetone, acrolein, 2-butanone, methacrolein, benzaldehyde, valeraldehyde, propionaldehyde, and m-methylbenzaldehyde, were diluted with acetonitrile to prepare a mixed standard solution with a concentration of 2.0 mg / L.

[0055] (3) Ultra-high performance liquid chromatography-ultraviolet detection: The obtained standard solution and sample solution are detected to obtain the chromatographic information of the standard solution and the chromatographic information of the sample test solution, respectively.

[0056] The conditions of ultra-high performance liquid chromatography-ultraviolet detection are as follows: RP C8 1.7um 2.1×150mm Column; water as mobile phase A, acetonitrile as mobile phase B, elution using mobile phase content and flow rate gradient changes; detection wavelength of 360nm; column temperature of 40°C; injection volume of 20μL.

[0057] The conditions of mobile phase content and flow rate gradient elution are shown in Table 1:

[0058] Table 1 Elution conditions

[0059] time Flow rate, mL / min Mobile phase A, % Mobile phase B, % 0-20min 0.2 60％→40％ 40％→60％ 20-30min 0.2 40％→0 60％→100％ 30-32min 0.2 0→60％ 100％→40％ 32-40min 0.2 60％ 40％

[0060] (4) Chromatographic information attribution: Based on the chromatographic information of the standard mixed solution obtained in step (3), the chromatographic information of the sample test solution was attributed. Table 2 shows the retention times of 10 aldehyde and ketone compounds, and Tables 3-4 show the test results of 10 batches of VOCs samples from super heavy oil processing stations.

[0061] Table 2 Retention times of 10 aldehydes and ketones

[0062] Compound Name Retention time (min) formaldehyde 7.686 Acetaldehyde 9.979 acetone 12.348 Acrolein 13.097 Propionaldehyde 13.958 2-Butanone 16.796 Methacrolein 17.383 Benzaldehyde 20.512 Valeraldehyde 21.604 m-Methacrolein 27.196

[0063] Table 3 Relative retention time (tR) min of common peaks of VOC samples from 10 batches of super heavy oil processing stations

[0064]

[0065]

[0066] Table 4 Relative peak areas of common peaks of VOC samples from 10 batches of super heavy oil processing stations (S)

[0067]

[0068] (4) Construction of reference fingerprint: Using the 2004A version of the "Chinese Medicine Chromatographic Fingerprint Similarity Evaluation System" published by the Chinese Pharmacopoeia Committee, the similarity calculation results of the chromatographic information of the sample test solution were calculated. The similarity calculation results of the 10 batches of VOC samples from the super-heavy oil treatment station and the standard fingerprint were: 0.984, 0.931, 0.957, 0.948, 0.921, 0.969, 0.942, 0.935, 0.950, 0.944. The overlapping spectra of 10 aldehyde and ketone compounds were obtained (see Appendix). Figure 1 ), reference fingerprint (attached Figure 2 ), the ratio of the peak area of ​​each fingerprint peak to the total peak area in the control fingerprint spectrum is greater than 0.5%.

[0069] 2. Methodological investigation

[0070] (1) Precision test

[0071] The first batch of samples were taken to prepare the test solution, and the sample was injected continuously for 6 times. The formaldehyde peak was used as the reference peak, and the RSD values ​​of the relative retention time and relative peak area of ​​the common peaks of 10 aldehyde and ketone compounds were calculated to be less than 3%, indicating that the instrument has good stability and precision. The specific test data are shown in Table 5-6.

[0072] Table 5 Retention time of 10 aldehydes and ketones after 6 consecutive injections (min)

[0073]

[0074]

[0075] Table 6 Peak area of ​​10 aldehyde and ketone compounds injected 6 times continuously Area (μV*sec)

[0076] Compound Name S1 S2 S3 S4 S5 S6 RSD(%) formaldehyde 174696 172780 173767 173003 175103 175108 0.60 Acetaldehyde 9505 9581 8971 9600 9616 9740 2.85 acetone 13780 14006 14274 13847 14765 14514 2.75 Acrolein 20677 20305 20041 20125 20569 20418 1.22 Propionaldehyde 16542 16573 15461 16272 16518 16311 2.58 2-Butanone 51769 52549 51188 49762 49082 52893 2.97 Methacrolein 56754 58372 57227 57296 58569 56572 1.44 Benzaldehyde 10500 10048 10738 10741 10456 10506 2.41 Valeraldehyde 17849 18550 18020 18187 18037 17966 1.36 m-Methacrolein 2805 2931 2807 2854 2917 2745 2.52

[0077] (2) Stability test

[0078] The first batch of samples were taken to prepare the test solution, and the samples were injected at 0, 2, 4, 6, 8, 10, 12, 14, 16, 18, and 24 hours respectively. The formaldehyde peak was used as the reference peak, and the RSD values ​​of the relative retention time and relative peak area of ​​the common peaks of 10 aldehyde and ketone compounds were calculated to be less than 3%, indicating that the test solution was stable within 18 hours. The test data are shown in Table 7-8.

[0079] Table 7 Retention time of 10 aldehydes and ketones at different injection times (min)

[0080]

[0081] Table 8 Peak area of ​​10 aldehyde and ketone compounds at different injection times (μV*sec)

[0082]

[0083]

[0084] (3) Reproducibility test

[0085] From the same batch of samples, 6 portions of test solution were precisely measured and injected separately. The formaldehyde peak was used as the reference peak. The RSD values ​​of the relative retention time and relative peak area of ​​the common peaks of 10 aldehyde and ketone compounds were calculated to be less than 3%, indicating that the method had good reproducibility. The test data are shown in Tables 9-10.

[0086] Table 9 Retention time of reproducibility test of 10 aldehydes and ketones (min)

[0087] Compound Name T1(min) T2(min) T3(min) T4(min) T5(min) T6(min) RSD(%) formaldehyde 7.808 7.818 7.813 7.820 7.818 7.818 0.06 Acetaldehyde 10.143 10.150 10.148 10.160 10.152 10.152 0.06 acetone 12.548 12.558 12.555 12.571 12.560 12.564 0.06 Acrolein 13.291 13.299 13.294 13.309 13.299 13.297 0.05 Propionaldehyde 14.160 14.177 14.170 14.180 14.176 14.176 0.05 2-Butanone 17.014 17.020 17.022 17.030 17.030 17.027 0.04 Methacrolein 17.593 17.601 17.605 17.613 17.608 17.606 0.04 Benzaldehyde 20.716 20.726 20.731 20.739 20.733 20.736 0.04 Valeraldehyde 21.813 21.823 21.829 21.839 21.834 21.835 0.04 m-Methacrolein 27.231 27.237 27.237 27.243 27.239 27.250 0.02

[0088] Table 10 Peak area of ​​10 aldehyde and ketone compounds in the current test (μV*sec)

[0089] Compound Name S1 S2 S3 S4 S5 S6 RSD(%) formaldehyde 843982 848700 849766 852443 844218 843787 0.43 Acetaldehyde 48779 49817 49834 49496 49076 49074 0.88 acetone 86099 87476 92026 89526 90746 88738 2.42 Acrolein 89232 87975 85471 83399 84626 88169 2.67 Propionaldehyde 78825 73150 75329 78291 76926 77752 2.78 2-Butanone 248783 248560 251659 257278 246588 249244 1.50 Methacrolein 313189 306824 304072 296384 306863 306298 1.78 Benzaldehyde 76147 72509 75381 76853 76782 76758 2.22 Valeraldehyde 92973 93926 90818 95610 94857 95091 1.88 m-Methacrolein 6609 6794 6857 6501 6524 6552 2.26

[0090] Example 2

[0091] Construction of reference fingerprint of aldehyde and ketone compounds:

[0092] (1) Preparation of sample test solution: 10 batches of VOCs samples from the super-heavy oil treatment station were taken continuously, and a dual-gas constant-flow atmospheric sampler was used with a sampling flow rate of 580 mL / min and a sampling time of 100 min. The sample was connected to an ozone interference column and a sampling tube to automatically complete the sampling. The sampling tube was eluted and collected with 5 mL of acetonitrile and filtered with a 0.24 μm microporous filter membrane to obtain the sample test solution.

[0093] (2) Preparation of standard solutions: The standard solutions of 2,4-dinitrophenylhydrazone derivatives of 10 aldehydes and ketones, including formaldehyde, acetaldehyde, acetone, acrolein, 2-butanone, methacrolein, benzaldehyde, valeraldehyde, propionaldehyde, and m-methylbenzaldehyde, were diluted with acetonitrile to prepare a mixed standard solution with a concentration of 1.8 mg / L.

[0094] (3) Ultra-high performance liquid chromatography-ultraviolet detection: The obtained standard solution and sample solution are detected to obtain the chromatographic information of the standard solution and the chromatographic information of the sample test solution, respectively.

[0095] The conditions of ultra-high performance liquid chromatography-ultraviolet detection are as follows: RP C8 1.7um 2.1×150mm Column; water as mobile phase A, acetonitrile as mobile phase B, elution using mobile phase content and flow rate gradient changes; detection wavelength of 350nm; column temperature of 35°C; injection volume of 18μL.

[0096] The conditions of mobile phase content and flow rate gradient elution are shown in Table 11:

[0097] Table 11 Elution conditions

[0098] time Flow rate, mL / min Mobile phase A, % Mobile phase B, % 0-20min 0.4 60％→40％ 40％→60％ 20-30min 0.4 40％→0 60％→100％ 30-32min 0.4 0→60％ 100％→40％ 32-40min 0.4 60％ 40％

[0099] (4) Chromatographic information attribution: Based on the chromatographic information of the standard mixed solution obtained in step (3), the chromatographic information of the obtained sample test solution was attributed, as shown in Table 12.

[0100] Table 12: Information on standard solutions and sample test solutions

[0101]

[0102] (5) Construction of reference fingerprint: The similarity calculation of the chromatographic information of the sample test solution was performed using the "Similarity Evaluation System of Chromatographic Fingerprint of Traditional Chinese Medicine" 2004A version published by the Chinese Pharmacopoeia Committee. The similarity calculation results of the 10 batches of VOCs samples from the super-heavy oil treatment station and the standard fingerprint were: 0.941, 0.956, 0.959, 0.978, 0.922, 0.985, 0.938, 0.961, 0.958, 0.972. Overlapping spectra and reference fingerprints of 10 aldehyde and ketone compounds were obtained. The ratio of the peak area of ​​each fingerprint peak to the total peak area in the reference fingerprint was greater than 0.5%.

[0103] Example 3

[0104] Construction of reference fingerprint of aldehyde and ketone compounds:

[0105] (1) Preparation of sample test solution: 10 batches of VOCs samples from the super-heavy oil treatment station were continuously taken using a dual-gas constant-flow atmospheric sampler with a sampling flow rate of 620 mL / min and a sampling time of 98 min. The sample was connected to an ozone interference column and a sampling tube to automatically complete the sampling. The sampling tube was eluted and collected with 5 mL of acetonitrile and filtered with a 0.24 μm microporous filter membrane to obtain the sample test solution.

[0106] (2) Preparation of standard solutions: The standard solutions of 2,4-dinitrophenylhydrazone derivatives of 10 aldehydes and ketones, including formaldehyde, acetaldehyde, acetone, acrolein, 2-butanone, methacrolein, benzaldehyde, valeraldehyde, propionaldehyde, and m-methylbenzaldehyde, were diluted with acetonitrile to prepare a mixed standard solution with a concentration of 2.2 mg / L.

[0107] (3) Ultra-high performance liquid chromatography-ultraviolet detection: The obtained standard solution and sample solution are detected to obtain the chromatographic information of the standard solution and the chromatographic information of the sample test solution, respectively.

[0108] The conditions of ultra-high performance liquid chromatography-ultraviolet detection are as follows: RP C8 1.7um 2.1×150mm Column; water as mobile phase A, acetonitrile as mobile phase B, elution with mobile phase content and flow rate gradient change; detection wavelength of 3700nm; column temperature of 30°C; injection volume of 22μL.

[0109] The conditions of mobile phase content and flow rate gradient elution are shown in Table 13:

[0110] Table 13 Elution conditions

[0111] time Flow rate, mL / min Mobile phase A, % Mobile phase B, % 0-20min 0.2 60％→40％ 40％→60％ 20-30min 0.2 40％→0 60％→100％ 30-32min 0.4 0→60％ 100％→40％ 32-40min 0.4 60％ 40％

[0112] (4) Chromatographic information attribution: Based on the chromatographic information of the standard mixed solution obtained in step (3), the chromatographic information of the obtained sample test solution was attributed, as shown in Table 14.

[0113] Table 14: Information on standard solutions and sample test solutions

[0114]

[0115]

[0116] (5) Construction of reference fingerprint: The similarity calculation of the chromatographic information of the sample test solution was performed using the "Similarity Evaluation System of Chromatographic Fingerprint of Traditional Chinese Medicine" 2004A version published by the Chinese Pharmacopoeia Committee. The similarity calculation results of the 10 batches of VOCs samples from the super-heavy oil treatment station and the standard fingerprint were: 0.971, 0.968, 0.932, 0.922, 0.951, 0.917, 0.950, 0.943, 0.967, 0.939. Overlapping spectra and reference fingerprints of 10 aldehyde and ketone compounds were obtained. The ratio of the peak area of ​​each fingerprint peak to the total peak area in the reference fingerprint was greater than 0.5%.

[0117] Example 4 Application of the comparative fingerprint of aldehyde and ketone compounds

[0118] (1) A dual-gas-path constant-flow atmospheric sampler was used with a sampling flow rate of 600 mL / min and a sampling time of 99 min. The sample was connected to an ozone-removing interference column and a sampling tube to automatically complete the sampling, which was unknown sample 1. The sampling tube was eluted and collected with 5 mL of acetonitrile and filtered with a 0.22 μm microporous filter membrane to obtain the solution to be tested.

[0119] (2) Ultra-high performance liquid chromatography-ultraviolet detection to obtain VOCs aldehyde and ketone chromatographic information, such as Figure 4 As shown in Table 15.

[0120] (3) Using the VOCs aldehydes and ketones reference fingerprint obtained in Example 1 as a reference, the obtained VOCs aldehydes and ketones chromatographic information was compared and determined, such as Figure 3 As shown in Table 16. The similarity between the VOCs aldehydes and ketones of the unknown sample and the control fingerprint is greater than 0.9, and it is determined that the pollution source of the unknown sample is the super-heavy oil processing station.

[0121] Table 15 Unknown sample 1 peak results

[0122]

[0123]

[0124] Table 16 Similarity analysis of unknown sample 1

[0125]

[0126] Example 5 Application of the comparative fingerprint of aldehyde and ketone compounds

[0127] (1) A dual-gas-path constant-flow atmospheric sampler was used with a sampling flow rate of 600 mL / min and a sampling time of 99 min. The sample was connected to an ozone-removing interference column and a sampling tube to automatically complete the sampling of unknown sample 2. The sampling tube was eluted and collected with 5 mL of acetonitrile and filtered with a 0.22 μm microporous filter membrane to obtain the solution to be tested.

[0128] (2) Ultra-high performance liquid chromatography-ultraviolet detection to obtain VOCs aldehyde and ketone chromatographic information such as Figure 5 As shown in Table 17.

[0129] (3) Using the VOCs aldehydes and ketones reference fingerprint obtained in Example 1 as a reference, the obtained VOCs aldehydes and ketones chromatographic information was compared and determined, as shown in Table 18. The similarity between the VOCs aldehydes and ketones of the unknown sample and the reference fingerprint was less than 0.9, as shown in Table 16, and it was determined that the pollution source of the unknown sample was not from the super heavy oil processing station.

[0130] Table 17 Unknown sample 2 peak results

[0131]

[0132] Table 18 Similarity analysis of unknown sample 2

[0133]

[0134] The above detailed description is a specific description of one feasible embodiment of the present invention. The embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not deviate from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A method for constructing a fingerprint of volatile aldehyde and ketone compounds, characterized in that: The following steps are involved: (1) preparing a sample test solution and a standard solution respectively, and performing ultra-high performance liquid chromatography-ultraviolet detection to obtain chromatographic information of the sample test solution and chromatographic information of the standard solution; (2) Using the chromatographic information of the standard solution as a reference, the chromatographic information of the sample solution is attributed, and the similarity of the chromatographic information of the sample solution is calculated to obtain a fingerprint of volatile aldehyde and ketone compounds; The aldehyde and ketone compounds are selected from at least eight of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, methacrolein, 2-butanone, n-butyraldehyde, benzaldehyde, valeraldehyde, m-methylbenzaldehyde and acetaldehyde.

2. The construction method according to claim 1, characterized in that: The preparation of the sample test solution in step (1) comprises: sampling by using an atmospheric sampler, eluting and collecting, and then filtering with a filter membrane to obtain the sample solution.

3. The construction method according to claim 2, characterized in that: The atmospheric sampler is a dual-gas-path constant-flow atmospheric sampler; the sampling flow rate is 580-620 mL / min, and the sampling time is 98-100 min.

4. The construction method according to claim 2, characterized in that: The elution solvent is acetonitrile; the filter membrane is a 0.20-0.24 μm microporous filter membrane.

5. The construction method according to claim 1, characterized in that: The preparation of the standard solution in step (1) comprises: diluting a solution of a 2,4-dinitrophenylhydrazone derivative of an aldehyde or ketone compound to obtain the standard solution.

6. The construction method according to claim 5, characterized in that: The reagent used for the dilution is acetonitrile; the concentration of the diluted standard solution is 1.8-2.2 mg / L.

7. The construction method according to claim 1, characterized in that: The conditions of ultra-high performance liquid chromatography-ultraviolet detection in step (1) are: reverse phase alkyl chromatographic column, mobile phase A is water, mobile phase B is acetonitrile, gradient elution; detection wavelength is 350-370nm; column temperature is 30-40°C; injection volume is 18-22μL, flow rate is 0.2-0.4mL / min.

8. The construction method according to claim 7, characterized in that: The gradient elution conditions are: 0min, mobile phase A: 55%-65%; mobile phase B: 35%-45%; 20min, mobile phase A: 35%-45%; mobile phase B: 55%-65%; 30 min, mobile phase A: 0%-5%; mobile phase B: 95%-100%; 32min, mobile phase A: 55%-65%; mobile phase B: 35%-45%; 40min, mobile phase A: 58%-62%; mobile phase B: 38-42%.

9. The construction method according to claim 7, characterized in that: The reverse phase alkyl chromatography column is RP C8 1.7um 2.1×150mm Column.

10. A fingerprint constructed by the construction method according to any one of claims 1 to 9, characterized in that: The ratio of the peak area of ​​each fingerprint peak to the total peak area in the fingerprint spectrum is greater than 0.5%.

11. Use of a fingerprint spectrum constructed by the construction method according to any one of claims 1 to 9 in determining whether the source of volatile organic compound pollution comes from an ultra-heavy oil processing station.

12. The use according to claim 11, characterized in that: The following steps are involved: (1) Sampling volatile aldehyde and ketone compound samples of unknown origin and preparing sample test solutions; (2) Ultra-high performance liquid chromatography-ultraviolet detection to obtain chromatographic information of volatile aldehydes and ketones of unknown origin; (3) Using the fingerprint of volatile aldehydes and ketones as a benchmark, the chromatographic information of volatile aldehydes and ketones of unknown origin is compared and determined.

13. The use according to claim 12, characterized in that: The judgment standard in step (3) is: if the chromatographic information of the volatile aldehyde and ketone compounds of the unknown sample is consistent with the reference fingerprint of the volatile aldehyde and ketone compounds, it can be determined that the pollution source of the unknown sample comes from the super-heavy oil processing station; On the contrary, it can be determined that the contamination source of the unknown sample is not from the super-heavy oil processing station.

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