A reactive organic compound comprehensive source analysis method, device and storage medium

Abstract

The application provides a reactive organic matter (ROGs) comprehensive source analysis method, equipment and a storage medium, and the method comprises the following steps: reactive organic matter data set acquisition, analysis and distribution of primary emission and secondary generation of reactive organic matter, primary emission source analysis of the secondary generation part, and ROGs comprehensive source analysis. The application solves the problem that the existing orthogonal matrix factorization (PMF) and other receptor source analysis methods cannot analyze and identify the primary emission source of the chemical conversion generated ROGs in the atmosphere based on the ROGs environmental observation concentration. The method of the application realizes the identification and quantification of the primary emission source of the secondary ROGs factor and its contribution rate on the basis of the PMF model result, so that the comprehensive emission source and contribution of the environmental atmospheric ROGs are obtained, and more accurate support is provided for precise control. The application also provides equipment and a storage medium for realizing the above-mentioned analysis method.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of environmental pollutant source analysis, in particular to a reactive organic compound source analysis method, device and storage medium. BACKGROUND

[0002] Reactive organic compounds (ROGs) are very complex as key precursor sources, including primary emissions and secondary generation. Primary sources include natural or man-made emission sources such as plant emission sources, motor vehicle exhaust, petrochemical industry, solvent use, etc. Secondary generation refers to the generation of ROGs such as aldehydes and ketones (OROGs) through atmospheric oxidation reactions of primary source emissions, and secondary generation accounts for a large proportion. Identifying the sources and relative contributions of ROGs is the key to precise control and management of ROGs.

[0003] The principal component matrix factorization (PMF) model is widely used in ROGs source tracking because it does not require input of detailed source composition spectrum of pollutants to identify various emission sources. It relies on mathematical indicators Q / Qexp, tracer components, and daily variations to achieve the purpose of identifying different primary sources. However, there is currently a lack of simple and effective methods to quantify the relative contribution of primary emissions to secondary generation. Therefore, there is an urgent need to develop related technologies and methods to achieve the source tracking of the secondary generation part of ROGs in the environment, and to provide technical and methodological support for the precise management of ROGs pollution in China. SUMMARY

[0004] The present application provides a comprehensive source analysis method for reactive organic compounds, which can use online measurement technology to determine reactive organic compounds in the air in real time, obtain high time resolution (within 1 hour) and accurate ROGs monitoring data, further based on receptor models and various source tracers, use the developed secondary ROGs factor and primary emission source parameterization algorithm, input constraint parameters, perform fitting operation and uncertainty evaluation, quickly separate the primary emission source and secondary generation part of ROGs in the atmosphere, and quantify the contribution rate of each primary emission source to the secondary generation part, thereby obtaining the true relative contribution of primary emission sources, which has important practical significance for precise prevention and control.

[0005] The present application provides a comprehensive source analysis method for reactive organic compounds, which comprises the following steps:

[0006] S1: Obtain a reactive organic compound data set by using online measurement technology to synchronously and continuously observe reactive organic compounds in the air to obtain online data of reactive organic compounds;

[0007] S2: Analysis of the primary and secondary generation of reactive organic matter: input data files and run the receptor model to obtain the receptor model output results; the output results include at least a plurality of primary emission source spectra and a secondary generation source spectrum and their relative contributions to the total concentration of reactive organic matter;

[0008] The primary emission source spectrum refers to the composition characteristics of reactive organic matter directly emitted by pollution sources such as motor vehicle emissions, process emissions, solvent use, etc.; the secondary generation source spectrum refers to the composition characteristics of reactive organic matter generated by atmospheric oxidation of substances emitted by primary emission sources.

[0009] S3: Analysis of the primary emission sources of the secondary generation part: based on the output results of the receptor model, a parameterization algorithm of secondary ROGs factors and primary emission sources is developed to finely analyze the contribution rate of various primary emission sources to secondary ROGs factors, which specifically includes: inputting non-methane hydrocarbon (NMHCs) source spectrum data and the corresponding OH reaction rate constant of the source spectrum species; setting the parameter conditions, taking the reaction time of each primary emission source spectrum as an unknown quantity, and obtaining it after model operation; according to the reactive organic matter source spectrum data, the corresponding OH reaction rate constant of the source spectrum species, and the reaction time, the relative contribution of the primary emission source to the secondary ROGs factor and the relative contribution of the background to the secondary ROGs factor are calculated; the secondary ROGs factor refers to the abundance characteristics of each reactive organic matter in the secondary generation source spectrum.

[0010] The NMHCs source spectrum data refers to the source spectrum obtained by selecting non-methane hydrocarbons and re-normalizing the source spectrum containing all measured reactive organic components in the primary and secondary source spectra output in S2.

[0011] The reaction time refers to the time from the emission of reactive organic matter from the emission source to the transmission to the observation point for detection. During this period, the reactive organic matter will undergo atmospheric chemical reactions in the atmosphere, so it is called reaction time.

[0012] S4: Comprehensive source analysis: comprehensively analyze the source analysis results of the receptor model in S2 and the primary emission source analysis results of the secondary ROGs factor in S3 to obtain more accurate relative contributions of primary emission sources to reactive organic matter and more accurately identify and determine the key source classes and potential contributions of reactive organic matter.

[0013] Preferably, the online data of the reactive organic matter is realized by online measurement technology, and the online measurement technology includes one or more of gas chromatography mass spectrometer (GC-MS / FID), proton transfer reaction time-of-flight mass spectrometer (PTR-TOF), and the time resolution is within 1 hour. High time resolution accuracy is beneficial to source analysis and identification, and preferably the time resolution is within 1 hour.

[0014] The receptor model is a positive matrix factorization receptor model (PMF).

[0015] Further, the data file of the receptor model comprises the following source tracer components: secondary components, primary artificial source tracer components and natural source tracer components. The secondary components refer to components generated by atmospheric oxidation reactions, the primary artificial source tracer components refer to specific organic components emitted by a certain artificial source, which can indicate the emission characteristics of the artificial source, and the natural source tracer components refer to specific organic components emitted by a natural source, which can indicate the emission characteristics of the natural source.

[0016] In order to improve the accuracy of the comprehensive source analysis of reactive organic matter, the secondary components comprise four or more of formaldehyde, acetone, peroxyacetyl nitrate (PAN), formic acid, cresol and benzoic acid, the primary artificial source tracer components comprise seven or more of propane, butane, pentane, acetonitrile, acetylene, ethylene, propylene, benzene, toluene, xylene, styrene and naphthalene, and the natural source tracer components comprise two or more of isoprene, terpene, methylacrolein (MACR) and methyl vinyl ketone (MVK).

[0017] The more the types of compounds in each component, the more accurate the comprehensive source analysis of reactive organic matter. Preferably, the secondary components comprise formaldehyde, acetone, peroxyacetyl nitrate (PAN), formic acid, cresol and benzoic acid, the primary artificial source tracer components comprise propane, butane, pentane, acetonitrile, acetylene, ethylene, propylene, benzene, toluene, xylene, styrene and naphthalene, and the natural source tracer components comprise isoprene, terpene, methylacrolein (MACR) and methyl vinyl ketone (MVK).

[0018] The receptor model is one of a positive matrix factorization (PMF) or a multilinear engine (ME2) that can effectively analyze a plurality of primary emission source factors (P1, P2, …, P n ) and a secondary generation factor P0.

[0019] The processing process of the NMHC source spectrum data input when the parameterization algorithm of the secondary ROGs factor and the primary emission source is run is as follows: extracting the NMHCs in each factor spectrum output by the receptor model and performing normalization processing to obtain the primary emission source factors (P ＊ 1, P ＊ 2, …, P ＊ n ) and the secondary source factor P ＊ 0 after processing.

[0020] The operation secondary ROGs factor and the parameterization algorithm of the primary emission source are set with the parameter conditions, including taking the reaction time (t1, t2,..., tn) of each primary emission source factor as unknown quantity, obtaining after model operation, and the model operation includes fitting of the following formula: n

[0021]

[0022] RP ＊ i (i=1, 2,..., n) is the source spectrum P * i The spectrum after reaction t i (i=1, 2,..., n) seconds; F i (i=1, 2,..., n) is the relative contribution of each factor in the receptor model output result; K OH is the OH reaction rate constant corresponding to the species in the source spectrum, and P ＊ 1, P ＊ 2,..., P ＊ n , P * 0 is one-dimensional data with the same number of elements; C OH is the measured concentration of OH free radicals during the observation period; and the reaction time needs to be inputted with a constraint range.

[0023] The step of calculating the relative contribution of the primary source spectrum to the secondary ROGs factor (F 0-1 , F 0-2 ,..., F 0-n ) and the relative contribution of the background to the secondary ROGs factor (F 0-Bg ) is:

[0024] First, the spectrum after reaction t i seconds of each primary emission source and the background spectrum are calculated,

[0025]

[0026] Further, the contribution of the primary emission source spectrum and the background to the secondary ROGs factor is calculated,

[0027]

[0028] RP i (i=1, 2,..., n) is the source spectrum P i The spectrum after reaction t i (i=1, 2,..., n) seconds, t i is obtained by fitting in the previous step; [RP1], [RP2],..., [RP n ​[P0], [Bg] represent the source spectra RP1, RP2, ..., RP3 respectively. n The summation of reactive organic components in P0 and Bg.

[0029] The combined source apportionment results of the receptor model in S2 and the primary emission source apportionment results of the secondary ROGs factor in S3 provide a more accurate calculation method for the relative contribution of primary emission sources to reactive organic matter.

[0030] The method is as follows:

[0031] F′1=F1+F 0-1

[0032] F′2=F2+F 0-2

[0033] ...

[0034] F′ n =F n +F 0-n

[0035] Where F1′, F2′, ..., F n ′ represent the relative contributions of primary emission source 1, primary emission source 2, ..., primary emission source n to the secondary ROGs factor.

[0036] To implement the above-described method for comprehensive source analysis of reactive organic compounds, this application provides a computer device, including: a memory and a processor; the memory is used to store a computer program; the processor is used to execute the computer program stored in the memory, so that the device performs the method described above. In the computer device, the number of the memory and the processor can be one or more.

[0037] The processor in the computer device loads one or more instructions corresponding to the processes of an application into memory, and the processor runs the application stored in memory, thereby realizing the analysis of the comprehensive sources of reactive organic compounds.

[0038] The memory may include random access memory (RAM) or non-volatile memory, such as at least one disk storage device. The memory stores an operating system and operating instructions, executable modules or data structures, or subsets thereof, or extended sets thereof. The operating instructions may include various operation instructions for implementing various operations. The operating system may include various system programs for implementing various basic business functions and handling hardware-based tasks.

[0039] The processor can be a general processor, including a central processing unit (CPU), a network processor (NP), etc.; can also be a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, a discrete gate or transistor logic device, a discrete hardware component.

[0040] The various components of the computer device can be coupled together by a bus system, which can include, in addition to a data bus, a power bus, a control bus, and a state signal bus, etc.

[0041] To achieve the above-mentioned reactive organic matter comprehensive source analysis method, the present application also provides a computer readable storage medium, which stores a computer program, and the program is executed by a processor to realize the method as described above. The storage medium includes ROM, RAM, magnetic disc or optical disc and various storage program codes. The effect of the present application is that the existing PMF receptor model can only realize the analysis of each primary source, and the secondary generation of ROGs is mainly from which primary emission source. The present study further quantifies the primary source contribution rate of the secondary part of ROGs based on the PMF model results, so as to obtain a more real primary emission source relative contribution, and provide more accurate support for precise control. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 The present application is a reactive organic matter comprehensive source analysis method.

[0043] Figure 2 The present application is a reactive organic matter comprehensive source analysis method. DETAILED DESCRIPTION

[0044] The present application is further illustrated by the following examples, but the present application is not limited to the scope of the examples. Any technology realized based on the above-mentioned content of the present application belongs to the scope of the present application. For those skilled in the art, other modifications can be easily realized, and therefore the present application is not limited to specific details without departing from the general concept defined by the claims and the equivalent scope. The present application is not limited to the specific details.

[0045] The following, unless otherwise indicated, contain the numbers in the specification.

[0046] Example 1

[0047] The present embodiment is further described in detail with reference to the drawings, taking the comprehensive source analysis of reactive organic compounds in the atmosphere of the suburbs in late spring and early summer as an example.

[0048] The method for analyzing the comprehensive source of reactive organic compounds in the atmosphere provided by the present application is implemented as follows:

[0049] Step one: reactive organic compound measurement: the sampling equipment is PTR-TOF, the sampling point is a typical suburban point in the Yangtze River Delta, surrounded by farmland and residents, located in the downwind of the city, the sampling time is 20 days, the time resolution is 5 minutes, 56 qualitative and quantitative species are collected, and 288 data of each species are collected.

[0050] Step two: identification based on the receptor model: the species name is used as the column label, and the time is used as the row label, and the observed concentration data is arranged into a 288x56 matrix; the uncertainty matrix is calculated by multiplying the concentration by 15%, and is also a 288x56 matrix. Input the two data files into the PMF receptor model, set the parameters, run, and combine the tracer components, finally output 5 source spectra (see Table 1): natural source, motor vehicle and industrial source, field burning source, household burning source and secondary human source, which contribute to the total mass of reactive organic compounds in the atmosphere by 6.2%, 31.3%, 15.5%, 23.8% and 23.2% respectively.

[0051] Table 1, source spectrum (unit: micrograms per cubic meter) and K analyzed by PMF receptor model OH

[0052]

[0053]

[0054] Step three: After screening out the hydrocarbons (marker species in Table 1) in each source spectrum in Table 1, normalization is performed, and the normalized source spectrum and the corresponding KoH are input into the secondary ROGs factor and primary emission source parameterization algorithm, the reaction time is constrained within half a day, and the reaction times of motor vehicle and industrial sources, field combustion sources and household combustion sources are 8h, 1h and 12h respectively, and the contributions of the secondary source ROGs mass are 42.3%, 24.7% and 19.9% respectively, and the background contribution is 13.1%.

[0055] Step four: Based on the results of steps two and three, the contributions of natural sources, motor vehicle and industrial sources, field combustion sources and household combustion sources to the total mass of reactive organic matter in the atmosphere are 6.2%, 41.0% (= 31.3% + 42% x 23.2%), 21.2% (= 15.5% + 24.7% x 23.2%) and 28.4% (= 23.8% + 19.9% x 23.2%) respectively.

[0056] The embodiment provides a computer device to realize the above-mentioned comprehensive source analysis of reactive organic matter. The computer device comprises a memory and a processor. The memory is used to store a computer program. The processor is used to execute the computer program stored in the memory, so that the device executes the above-mentioned method.

[0057] The embodiment also provides a computer readable storage medium, which stores a computer program. When the processor executes the computer program, the above-mentioned method is realized.

Claims

1. A method for comprehensive source analysis of reactive organic compounds, characterized in that, The method comprises the following steps: S1, reactive organic matter data set acquisition: using online measurement technology, synchronously and continuously observing reactive organic matters in the air to obtain online data of the reactive organic matters; S2, analytical distribution of primary emission and secondary generation of reactive organic matters: input data file and run receptor model to obtain receptor model output result; the output result at least includes a plurality of primary emission source factors and a secondary generation factor, and their relative contributions; the receptor model is one of orthogonal matrix factor decomposition or multi-linear engine ME2 which can effectively analyze a plurality of primary emission source factors P1, P2,..., P n and secondary generation factor P0. S3, the secondary generation factor is analyzed: based on the output results of the receptor model, the contribution rate of various primary emission sources to the secondary generation factor is analyzed by developing a parameterization algorithm of the secondary generation factor and the primary emission source, including: inputting non-methane hydrocarbon source spectrum data and OH reaction rate constant corresponding to source spectrum species; setting parameter conditions, taking the reaction time of each primary emission source factor as an unknown quantity, and obtaining it after model operation; according to the reactivity of organic source spectrum data, OH reaction rate constant corresponding to source spectrum species and reaction time, calculating the relative contribution of primary emission source to secondary generation factor and the relative contribution of background to secondary generation factor; the processing process of non-methane hydrocarbon source spectrum data input into the parameterization algorithm of the secondary generation factor and the primary emission source is: extracting non-methane hydrocarbon in each factor spectrum output by the receptor model and performing normalization processing to obtain the processed primary emission source factor P * 1, P * 2,..., P * n and secondary generation factor P * 0; S4, comprehensive source analysis: comprehensively analyzing the source analysis results of the receptor model in S2 and the secondary generation factor in S3 to obtain more accurate relative contributions of primary emission sources to the reactive organic matters, and more accurately identifying and determining key source classes and potential contributions of the reactive organic matters.

2. The reactive organic compound comprehensive source analysis method according to claim 1, characterized by, The online measurement technology comprises one or more of gas chromatography mass spectrometers, proton transfer reaction time-of-flight mass spectrometers, and the like, and the time resolution is within 1 hour.

3. The reactive organic compound comprehensive source analysis method according to claim 1, characterized by, The data file of the receptor model comprises source tracer components, wherein the source tracer components comprise four or more of formaldehyde, acetone, peroxyacetyl nitrate, formic acid, cresol, and benzoic acid, seven or more of propane, butane, pentane, acetonitrile, acetylene, ethylene, propylene, benzene, toluene, xylene, styrene, and naphthalene, and two or more of isoprene, terpene, methyl propyl aldehyde, and methyl vinyl ketone.

4. A computer device, comprising: The device comprises a memory and a processor, the memory is used for storing a computer program, and the processor is used for executing the computer program stored in the memory to enable the device to execute the method according to any one of claims 1-3.

5. A computer-readable storage medium having stored thereon a computer program, characterized in that, The computer program is executed by the processor to implement the method according to any one of claims 1-3.

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