Cycloalkane separation method, computer program product and cycloalkane detection system

Abstract

The invention provides a cycloalkane separation method, a computer program product and a cycloalkane detection system. The method comprises the steps that a detection device is controlled to separate compounds, the one-dimensional retention time of all the compounds in a one-dimensional chromatographic column is obtained, the two-dimensional retention time of all the compounds in a two-dimensional chromatographic column is obtained, the one-dimensional retention time is the time needed for separating out the compounds through the one-dimensional chromatographic column, and the two-dimensional retention time is the time needed for separating out the compounds through the two-dimensional chromatographic column. The two-dimensional retention time is the time required for separating the compound by the two-dimensional chromatographic column; a target compound in the separated compounds is determined according to the one-dimensional retention time and the two-dimensional retention time of the separated compounds, and the target compound is cyclohexane or cyclopentane; the content of the target compound is obtained, the content is sent to target equipment, and the target equipment is equipment used by the target object, so that the target object is guided to improve the catalyst. According to the scheme, the problem that cycloalkanes (cyclohexane or cyclopentane) cannot be rapidly measured in the prior art is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of component analysis of coal direct liquefaction oil, in particular to a naphthene separation method, a naphthene detection system control device, a computer program product and a naphthene detection system. BACKGROUND

[0002] Coal direct liquefaction oil composition analysis generally has three aspects: 1) simple group composition analysis, which divides coal liquefaction oil into saturated hydrocarbons, aromatic hydrocarbons, or saturated hydrocarbons, aromatic hydrocarbons and resins through solid phase extraction, liquid extraction or analytical instruments, and then calculates the content of each part; 2) detailed group composition analysis, which can divide coal direct liquefaction oil into various groups according to SH / T 0606, such as saturated hydrocarbons into naphthene, dinaphthene, trinaphthene, etc., and aromatic hydrocarbons into alkylbenzene, dinaphthylbenzene, etc.; 3) molecular level composition, such as detailed compound type, carbon number distribution and molecular composition of monomer compounds. Molecular composition fundamentally determines the physicochemical properties and processing performance of coal direct liquefaction oil, so it is very important to comprehensively understand coal direct liquefaction oil from a deep level, and to process coal direct liquefaction oil and control the quality of coal direct liquefaction oil.

[0003] The analysis of n-alkyl substituted naphthene in coal direct liquefaction oil is a kind of molecular level characterization, and n-alkyl substituted naphthene refers to a single ring alkane with one substituted alkyl group in the naphthene, and the substituted alkane is a straight chain alkyl. In the composition of coal direct liquefaction oil, the parent structure of this kind of compound is mainly cyclopentane and cyclohexane, which has the common characteristics of n-alkane and naphthene, and the content directly affects the quality and utilization value of coal direct liquefaction oil. The traditional method needs large-scale experiments for measurement, and the process is complicated and time-consuming, so it is currently impossible to quickly determine naphthene (cyclohexane or cyclopentane), and a method for quickly determining naphthene (cyclohexane or cyclopentane) is urgently needed. SUMMARY

[0004] The main purpose of the present application is to provide a naphthene separation method, a naphthene detection system control device, a computer program product and a naphthene detection system, to at least solve the problem that naphthene (cyclohexane or cyclopentane) cannot be quickly determined in the prior art.

[0005] In order to achieve the above object, according to one aspect of the present application, a method for separating naphthenes is provided, which is applied to a naphthene detection system including a control device and a detection device, the control device being configured to control the detection device to separate compounds, the detection device including at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column being configured to separate a plurality of compounds according to differences in boiling points of the compounds, and the two-dimensional chromatographic column being configured to separate a plurality of compounds that cannot be separated by the one-dimensional chromatographic column according to differences in polarities of the compounds, the method including: controlling the detection device to separate the compounds, obtaining one-dimensional retention times of each of the compounds in the one-dimensional chromatographic column, and obtaining two-dimensional retention times of each of the compounds in the two-dimensional chromatographic column, wherein the one-dimensional retention time is a time required for the one-dimensional chromatographic column to separate the compound, and the two-dimensional retention time is a time required for the two-dimensional chromatographic column to separate the compound; determining a target compound among the separated compounds according to the one-dimensional retention times and the two-dimensional retention times of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane; obtaining a content of the target compound, and sending the content to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve a catalyst.

[0006] Optionally, determining the target compound among the separated compounds according to the one-dimensional retention times and the two-dimensional retention times of each of the separated compounds includes: determining a compound with the largest one-dimensional retention time as a first candidate compound, determining a compound with the largest one-dimensional retention time among the compounds other than the first candidate compound as a second candidate compound; in a case where the two-dimensional retention time of the first candidate compound is greater than the two-dimensional retention time of the second candidate compound, determining the first candidate compound as the cyclohexane and the second candidate compound as the cyclopentane; and in a case where the two-dimensional retention time of the first candidate compound is less than the two-dimensional retention time of the second candidate compound, determining the second candidate compound as the cyclohexane and the first candidate compound as the cyclopentane.

[0007] Optionally, determining the compound with the largest one-dimensional retention time as a first candidate compound, and determining the compound with the largest one-dimensional retention time among the compounds other than the first candidate compound as a second candidate compound, comprises: sorting a plurality of the one-dimensional retention times in descending order to obtain sorted one-dimensional retention times; extracting the first two one-dimensional retention times from the sorted one-dimensional retention times; calculating the difference between the first two one-dimensional retention times to obtain a retention time difference; and in the case that the retention time difference is less than or equal to a preset time threshold, determining the compound with the largest one-dimensional retention time among the first two one-dimensional retention times as the first candidate compound, and determining the other compound among the first two one-dimensional retention times as the second candidate compound among the compounds other than the first candidate compound.

[0008] Optionally, after calculating the difference between the first two one-dimensional retention times to obtain a retention time difference, the method further comprises: in the case that the retention time difference is greater than the preset time threshold, extracting the largest one-dimensional retention time from the sorted one-dimensional retention times to obtain a peak one-dimensional retention time; and determining the compound corresponding to the peak one-dimensional retention time as the cyclohexane and determining the content of the cyclopentane as 0.

[0009] Optionally, after determining the target compound among the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each separated compound, the method further comprises: calculating the mass fraction of the compound according to a target formula, and sending the mass fraction to the target device to guide the target object to improve the catalyst, wherein the target formula is:

[0010] ωi represents the mass fraction, mi represents the mass of the ith compound, m represents the total mass of all the compounds, and n represents the number of the compounds. i

[0011] ​Optionally, after obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, the method further comprises: constructing a table and displaying the table in a display interface, wherein the table at least includes a first column and a second column, the data in the first column is the one-dimensional retention time, and the data in the second column is the two-dimensional retention time; detecting and responding to a first operation to sort the one-dimensional retention time in the first column in descending or ascending order, wherein the first operation is used to sort the data in the first column; detecting and responding to a second operation to sort the two-dimensional retention time in the second column in descending or ascending order, wherein the second operation is used to sort the data in the second column; and displaying the sorted table in the display interface.

[0012] Optionally, after obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, the method further comprises: deleting data that is empty in the plurality of one-dimensional retention times; and deleting data that is empty in the plurality of two-dimensional retention times.

[0013] According to another aspect of the present application, a control device of a naphthene detection system is provided, the naphthene detection system comprising a control device and a detection device, the control device being configured to control the detection device to separate compounds, the detection device comprising at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column being configured to separate a plurality of the compounds according to differences in boiling points of the compounds, and the two-dimensional chromatographic column being configured to separate a plurality of the compounds that cannot be separated by the one-dimensional chromatographic column according to differences in polarities of the compounds, the device comprising: a first obtaining unit configured to control the detection device to separate the compounds, obtain one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column, and obtain two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, wherein the one-dimensional retention time is a time required for the one-dimensional chromatographic column to separate the compounds, and the two-dimensional retention time is a time required for the two-dimensional chromatographic column to separate the compounds; a determining unit configured to determine a target compound among the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane; and a processing unit configured to obtain a content of the target compound and send the content to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve a catalyst.

[0014] According to still another aspect of the present application, there is provided a computer program product comprising a computer program which, when executed by a processor, implements the steps of any one of the methods for separating naphthenes.

[0015] According to still another aspect of the present application, there is provided a naphthene detection system comprising a control device and a detection device, the control device being configured to control the detection device to separate compounds, the detection device comprising at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column being configured to separate a plurality of compounds according to differences in boiling points of the compounds, the two-dimensional chromatographic column being configured to separate a plurality of compounds that cannot be separated by the one-dimensional chromatographic column according to differences in polarities of the compounds, and the control device being configured to implement the steps of any one of the methods for separating naphthenes.

[0016] By using two chromatographic columns of the detection device to separate sample compounds, the one-dimensional chromatographic column separates the compounds based on differences in boiling points of the compounds, and compounds with different boiling points will exit the one-dimensional column at different time points, which is referred to as one-dimensional retention time. Subsequently, the compounds separated by the one-dimensional column are introduced into the two-dimensional column, and the two-dimensional column separates the compounds again according to differences in polarities of the compounds, and compounds with different polarities have different retention times on the two-dimensional column, which is referred to as two-dimensional retention time. Since cyclohexane and cyclopentane have high boiling points and high polarities, they can be quickly screened out by using the two retention times. Therefore, compared with traditional large-scale experiments, the present application can quickly screen and determine cyclohexane and cyclopentane by using the separation function of the detection device and the characteristics of cyclohexane and cyclopentane, and the determination speed is faster than that of the prior art. BRIEF DESCRIPTION OF DRAWINGS

[0017] The accompanying drawings, which form a part of the present application, are intended to provide further understanding of the present application and are incorporated herein for a purpose of explanations and are not intended as an improper limitation to the present application. In the drawings:

[0018] Figure 1 A hardware structure block diagram of a mobile terminal for performing a method for separating naphthenes is shown according to an embodiment provided by the present application;

[0019] Figure 2 A flowchart of a method for separating naphthenes is shown according to an embodiment provided by the present application;

[0020] Figure 3 A structure diagram of a detection device is shown;

[0021] Figure 4 A full two-dimensional spectrum of a naphthene after qualitative determination in coal direct liquefaction oil is shown;

[0022] Figure 5 A total two-dimensional profile of naphthenes in coal direct liquefaction oil on a hydrogen flame ionization detector is shown;

[0023] Figure 6 A total two-dimensional profile of n- substituted cyclohexane and n- substituted cyclopentane in coal direct liquefaction oil is shown;

[0024] Figure 7 A total two-dimensional profile of n- substituted naphthene standard on a hydrogen flame ionization detector is shown;

[0025] Figure 8 A structural block diagram of a control device of a naphthene detection system according to an embodiment of the present application is shown.

[0026] Among the above figures, the following reference signs are included:

[0027] 102, processor; 104, memory; 106, transmission device; 108, input and output device; 10, split sample inlet; 11, one-dimensional chromatographic column; 12, first stage modulator; 13, carrier gas inlet; 14, second stage modulator; 15, two-dimensional chromatographic column; 16, separator; 17, first damping column; 18, second damping column; 19, time-of-flight mass spectrometer detector; 20, hydrogen flame ionization detector. DETAILED DESCRIPTION

[0028] It should be noted that the embodiments and features in the present application can be combined with each other without conflict. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0029] In order to enable those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the present application.

[0030] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects and are not necessarily used to describe a specific order or sequential order. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present application described here. In addition, the terms "including" and "having" and any of their variations 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 necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0031] As described in the background technology, the prior art is unable to quickly determine cycloalkanes (cyclohexane or cyclopentane). To address the above problem, embodiments of the present application provide a method for separating cycloalkanes, a control device for a cycloalkane detection system, a computer program product, and a cycloalkane detection system.

[0032] The technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the accompanying drawings in the embodiments of the present invention.

[0033] The method embodiments provided in the embodiments of the present application can be executed in a mobile terminal, a computer terminal or a similar computing device. Taking running on a mobile terminal as an example, Figure 1 This is a hardware structure block diagram of a mobile terminal for a method for separating cycloalkanes according to an embodiment of the present invention. Figure 1 As shown, the mobile terminal may include one or more ( Figure 1 Only one is shown) a processor 102 (the processor 102 may include but is not limited to a microprocessor MCU or a programmable logic device FPGA and other processing devices) and a memory 104 for storing data, wherein the mobile terminal may also include a transmission device 106 and an input and output device 108 for communication functions. It will be understood by those skilled in the art that Figure 1 The structure shown is only for illustration and does not limit the structure of the mobile terminal. Figure 1 More or fewer components than shown, or with Figure 1 Different configurations shown.

[0034] The memory 104 can be used to store computer programs, such as software programs of application software and modules, such as a computer program corresponding to the method for separating naphthenes in the embodiments of the present application. The processor 102 can execute various functional applications and data processing, i.e., implement the above method, by running the computer program stored in the memory 104. The memory 104 can include a high-speed random access memory, and can further include a non-volatile memory, such as one or more magnetic storage devices, flash memories, or other non-volatile solid-state memories. In some examples, the memory 104 can further include memories disposed remotely with respect to the processor 102, which can be connected to the mobile terminal through a network. Examples of the above network include, but are not limited to, the Internet, an intranet, a local area network, a mobile communication network, and a combination thereof. The transmission device 106 is used to receive or send data via a network. The specific examples of the above network can include a wireless network provided by a communication provider of the mobile terminal. In one example, the transmission device 106 includes a network adapter (NIC), which can be connected to other network devices through a base station so as to communicate with the Internet. In one example, the transmission device 106 can be a radio frequency (RF) module, which is used to communicate with the Internet in a wireless manner.

[0035] In the embodiments, a method for separating naphthenes running on a mobile terminal, a computer terminal or a similar computing device is provided. It should be noted that the steps shown in the flowchart of the accompanying drawings can be executed in a computer system such as a set of computer executable instructions, and although a logical order is shown in the flowchart, in some cases, the steps shown or described can be executed in an order different from that shown here.

[0036] Figure 2 is a flowchart of the method for separating naphthenes according to the embodiments of the present application. As shown in Figure 2 the method includes the following steps:

[0037] In step S201, the detection device is controlled to separate the compounds, and one-dimensional retention times of each of the compounds in the one-dimensional chromatographic column and two-dimensional retention times of each of the compounds in the two-dimensional chromatographic column are obtained. The one-dimensional retention time is the time required for separating the compounds by the one-dimensional chromatographic column, and the two-dimensional retention time is the time required for separating the compounds by the two-dimensional chromatographic column.

[0038] Specifically, the coal direct liquefaction oil sample is injected into a comprehensive two-dimensional gas chromatography-time of flight mass spectrometer / hydrogen flame ionization detector (GCxGC-TOF MS / FID) system, and the detection device separates the compounds. The comprehensive two-dimensional gas chromatography technology combines the high separation capacity of one-dimensional and two-dimensional chromatographic columns, in which the one-dimensional column separates according to the boiling point, and the two-dimensional column separates according to the polarity, which can significantly distinguish the compounds with similar structures, especially naphthenes and their derivatives.

[0039] The data from the detection device is received, and the retention time of each compound on the one-dimensional and two-dimensional chromatographic columns is recorded, in which the one-dimensional retention time reflects the separation of different boiling point compounds, and the two-dimensional retention time reflects the separation of the same boiling point compounds under the difference in polarity. The retention time is a direct reflection of the physical and chemical properties of the compound, and by comparative analysis, the compounds with similar structures can be effectively distinguished. Since the retention behavior of naphthenes and their normal substitution derivatives on the column has consistency and regularity, the analysis of the retention time can accurately identify the positions of cyclohexane and cyclopentane in the spectrum.

[0040] Step S202, determining a target compound in the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane;

[0041] Specifically, the target compounds cyclohexane and cyclopentane have specific retention time rules on the comprehensive two-dimensional spectrum. Based on the "tile effect" analysis, cyclohexane and cyclopentane are located at the upper right corner of the "tile", and the two peaks with the longest one-dimensional retention time are usually normal substituted cyclohexane and cyclopentane. By comparing the approximate range of the two-dimensional retention time, it can be further determined which is cyclohexane and which is cyclopentane.

[0042] Step S203, obtaining the content of the target compound, and sending the content to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve the catalyst.

[0043] Specifically, the content of the target compound cyclohexane or cyclopentane is calculated by using the data collected by the hydrogen flame ionization detector (FID), and then the content information is sent to the target device, such as a catalyst preparation device or a reactor control system, through the communication interface of the control device.

[0044] When the target device receives the content data of the target compound (cyclohexane or cyclopentane), based on this information, the system can automatically or manually adjust the relevant parameters of the catalyst. For the catalyst preparation system, if it is found that the content of cyclohexane or cyclopentane is lower than expected, the device can optimize the catalyst performance by adjusting the metal load, the carrier type or introducing auxiliary agents, etc., in order to improve the output of the target compound. For the reactor control system, if the content information indicates that the output of the target compound is unstable, the reaction conditions such as temperature gradient, pressure or reaction time can be adjusted to create a more favorable environment for the generation of the target compound. To help the R&D team track the influence of different catalyst formulations or reaction conditions on the composition of the product, and provide data support for future catalyst development.

[0045] Through the embodiment, two chromatographic columns of the detection device are used to separate the sample compound. The one-dimensional chromatographic column preliminarily separates the compounds based on the boiling point difference of the compounds. The compounds with different boiling points will leave the one-dimensional column at different time points. This time is called one-dimensional retention time. Subsequently, the compounds preliminarily separated by the one-dimensional column are introduced into the two-dimensional column. The two-dimensional column separates the compounds again according to the polarity difference of the compounds. The compounds with different polarities have different retention times on the two-dimensional column. This time is called two-dimensional retention time. The boiling points of cyclohexane and cyclopentane are very high, and the polarities are also very high. Therefore, cyclohexane and cyclopentane can be quickly screened out through the two retention times. Therefore, compared with the traditional large-scale experiment for determination, the scheme can quickly screen and determine by combining the separation function of the detection device and the characteristics of cyclohexane and cyclopentane. Compared with the prior art, the determination speed is faster.

[0046] Specifically, the scheme provided in the present application is a method for rapidly determining n-substituted monocyclic alkanes in coal direct liquefaction oil, and more specifically, a method for rapidly determining n-substituted monocyclic alkanes in coal direct liquefaction oil by using a comprehensive two-dimensional gas chromatography-time of flight mass spectrometer / hydrogen flame ionization detector (GCxGC-TOF MS / FID). In the method, the peak appearance rule of n-substituted monocyclic alkanes in the comprehensive two-dimensional "tile effect" is applied to quickly determine the peak appearance position of n-substituted monocyclic alkanes, and qualitative and quantitative analysis is performed.

[0047] The analysis of n-substituted monocycloalkanes in coal direct liquefaction oil is a kind of molecular level characterization, and the n-substituted monocycloalkanes refer to monocycloalkanes with one substituted alkyl in the alkane, and the substituted alkane is a straight-chain alkyl. In the composition of coal direct liquefaction oil, the parent structures of this kind of compounds are mainly cyclopentane and cyclohexane, which have the common characteristics of n-alkanes and cycloalkanes, and the content directly affects the quality and utilization value of coal direct liquefaction oil. For example, the cetane number of oil depends on the chemical composition of the oil, and generally the cetane number of n-alkanes is the highest, followed by isomeric alkanes, and the cetane number of cycloalkanes is the lowest. The longer the side chain of cycloalkanes, the higher the cetane number. Therefore, the characterization of n-substituted monocycloalkanes has a good guiding effect on the coal direct liquefaction hydrogenation process and catalyst preparation process.

[0048] The comprehensive two-dimensional gas chromatography method is a new method that appeared in the 1990s, and is a kind of multi-dimensional chromatography method, but it is different from the commonly said two-dimensional chromatography (GC+GC). The comprehensive two-dimensional gas chromatography (GC×GC) is a two-dimensional gas chromatography formed by combining two chromatographic columns with different separation mechanisms and independent of each other by a modulator. Compared with the conventional gas chromatography, the comprehensive two-dimensional gas chromatography has the advantages of 20-50 times higher sensitivity than one-dimensional chromatography, high resolution, large peak capacity, good sensitivity, and strong regularity of spectrum distribution, and is widely used in molecular level characterization of oil.

[0049] The scheme of the present application adopts comprehensive two-dimensional gas chromatography-time of flight mass spectrometer / hydrogen flame ionization detector to complete the rapid detection of n-substituted monocycloalkanes in coal direct liquefaction oil. The method utilizes the characteristics of high separation capacity of comprehensive two-dimensional gas chromatography, and under specific analysis conditions, the different carbon number compounds of monocycloalkanes in coal direct liquefaction oil show a strong "tile effect", and then the special position of n-substituted monocycloalkanes on the "tile" is used to quickly lock n-substituted cyclohexane and n-substituted cyclopentane. The method provides two methods for determining n-substituted cyclohexane and n-substituted cyclopentane, which is simple and fast, reduces the data processing time of the analyst, and improves the work efficiency.

[0050] The above method is applied to a cycloalkane detection system, the cycloalkane detection system includes a control device and a detection device, the control device is used to control the separation of compounds by the detection device, the detection device includes at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column is used to separate a plurality of compounds according to the different boiling points of the compounds, and the two-dimensional chromatographic column is used to separate a plurality of compounds that cannot be separated by the one-dimensional chromatographic column according to the different polarities of the compounds.

[0051] Specifically, the instrument used in the scheme is comprehensive two-dimensional gas chromatography-time of flight mass spectrometer / hydrogen flame ionization detector (GC×GC-TOF MS / FID), i.e. the detection device.

[0052] Specifically, the detection device as shown comprises a split sample inlet 10, a one-dimensional chromatographic column 11, a first-stage modulator 12, a carrier gas inlet 13, a second-stage modulator 14, a two-dimensional chromatographic column 15, a separator 16, a first damping column 17, a second damping column 18, a time-of-flight mass spectrometer 19, and a hydrogen flame ionization detector 20. Figure 3 The sample to be detected is introduced through the split sample inlet, and the carrier gas is introduced through the carrier gas inlet; the sample to be detected is first separated by the one-dimensional chromatographic column, then periodically cold-focused in the first-stage modulator, then twice focused in the second-stage modulator, and then pulsed and radiated into the two-dimensional chromatographic column for two-dimensional separation; then, the separator (containing a Dean Switch module) divides the sample after the two-dimensional chromatographic column into two paths, one of which passes through the first damping column to enter the time-of-flight mass spectrometer, and the other of which passes through the second damping column to enter the hydrogen flame ionization detector. By adjusting the length and pressure of the damping column connecting the two detectors, the one-dimensional and two-dimensional peak times (peak positions) of the components on the two detectors are kept substantially consistent, so that the full two-dimensional gas chromatography-time-of-flight mass spectrometry spectrum and the result of the above full two-dimensional gas chromatography spectrum are related to each other.

[0053] Specifically, the full two-dimensional gas chromatography-time-of-flight mass spectrometer / hydrogen flame ionization detector (GCxGC-TOF MS / FID) is a brand-new separation and detection instrument. On the basis of the full two-dimensional gas chromatography-time-of-flight mass spectrometer (GCxGC-TOF MS), a Dean Switch module is added, and the coal direct liquefaction oil is divided into two paths after one-dimensional and two-dimensional separation, one of which enters the time-of-flight mass spectrometer (TOF MS), and the other of which enters the hydrogen flame ionization detector (FID). By adjusting the length and pressure of the damping column connecting the two detectors, the one-dimensional and two-dimensional peak times of the components on the two detectors are kept substantially consistent.

[0054] Specifically, the data collected by the time-of-flight mass spectrometer is used for qualitative analysis, and the data collected by the hydrogen flame ionization detector is used for quantitative analysis.

[0055] Specifically, the one-dimensional chromatographic column uses a non-polar chromatographic column HP-PONA (50m x 0.20mm x 0.50μm), and the two-dimensional chromatographic column uses a weakly polar chromatographic column Rxi-17Sil ms.

[0056]

[0057] ​Specifically, the full two-dimensional gas chromatography-time of flight mass spectrometry conditions are as follows: injection amount is 0.2-0.5 uL, split ratio is 100-300:1, injection port temperature is 290-320℃, carrier gas is He, column flow is constant flow mode, and flow rate is 1.0-2.0 mL / min; one-dimensional temperature programming is as follows: initial temperature is 50-60℃, holding time is 1.0-5.0 min, then increasing to 315℃ at a rate of 1.0-2.0℃ / min, and holding time is 15.0-30 min; two-dimensional compensation temperature is 5-15℃, electron impact ionization (EI) source is used, bombardment voltage is 70 eV, solvent is not delayed, ion source temperature is 250℃, transmission line temperature is 280℃, and detector voltage is 1400 V.

[0058] Specifically, the data collected by time of flight mass spectrometry is used for qualitative analysis, and the qualitative analysis is combined with spectral library retrieval, standard substance retention value comparison, mass spectrum analysis, standard mass spectrum comparison, full two-dimensional spectrum characteristics and extraction of molecular ions of compounds.

[0059] Specifically, the standard mass spectrum comparison method is used for qualitative analysis, and the mass spectrum characteristics of naphthenes are referred to. The main fragment ions of naphthenes are caused by σ-broken ring fragmentation, H rearrangement after ring opening, and rd-reaction, to generate [M-C n H 2n+1 ] +● series (m / z 41, 55, 69, 83, 97……) even-electron ions; another reaction path of naphthene fragmentation is ring opening, followed by ɑ-reaction or rd-reaction, to generate [M-C2H4] +● ion and [M-C n H 2n ] +● series (m / z 42, 56, 70, 84, 96……) odd-electron ions.

[0060] Specifically, the extraction of molecular ions of compounds is used for qualitative analysis, and the mass spectrum characteristics of normal substituted naphthenes are referred to. The normal substituted naphthenes have very significant parent ring characteristic fragment ions regardless of the length of the alkyl chain, such as m / z 69 is cyclopentane, m / z 83 is cyclohexane, and with the increase of one alkyl substitution, the largest alkyl group is preferentially lost, and the charge is retained on the parent ring with a small alkyl group, and the cyclopentane is m / z 69, 83, 97……, and the cyclohexane is m / z 83, 97, 111…….

[0061] Specifically, the full two-dimensional spectrum characteristics method is used for qualitative analysis, and the naphthenes in the coal direct liquefaction oil show a “tile effect” on the full two-dimensional spectrum: the compounds with the same molecular weight show a diagonal upward distribution and a cluster with the increase of boiling point and polarity; and the compounds with different relative molecular masses show a significant tile effect with the increase of molecular mass.

[0062] Specifically, the data collected by time-of-flight mass spectrometry is qualitatively adopted, and the monocyclic alkanes after qualitative identification are classified as C5-CnH2n, C6-CnH2n, C7-CnH2n, C8-CnH2n, and so on.

[0063] Specifically, the monocyclic alkanes after qualitative identification are classified as C5-CnH2n, C6-CnH2n, C7-CnH2n, C8-CnH2n, and so on. Wherein Cn refers to the total carbon number of the compound, CnH2n is the molecular formula thereof, for example, the total carbon number of cyclopentane is 5, and the molecular formula is C5H10, which is classified as C5-CnH2n; the total carbon number of methylcyclopentane and cyclohexane is 6, and the molecular formula is C6H12, which is classified as C6-CnH2n; and the like.

[0064] Specifically, after the qualitative identification and classification of monocyclic alkanes in the coal direct liquefaction oil are completed, a classification method is edited, and the classification method is applied to the data collected by the hydrogen flame ionization detector to obtain the distribution diagram and distribution data of monocyclic alkanes in the coal direct liquefaction oil on the hydrogen flame ionization detector.

[0065] Specifically, the method aims to realize efficient separation and content determination of naphthenes in complex mixtures through full two-dimensional gas chromatography technology. The control device and the detection device form the main part of the naphthene detection system and form an automatic control detection process. The control device receives preset parameters such as column temperature, pressure, and flow rate, and accurately controls the separation conditions of the detection device. The non-polar characteristics of the one-dimensional chromatographic column are used for preliminary separation, and then the weak polar characteristics of the two-dimensional chromatographic column are used for secondary separation.

[0066] The non-polar column as a one-dimensional chromatographic column is suitable for the preliminary separation of compounds with large differences in boiling points. Compounds with high boiling points have long retention times, and compounds with low boiling points have short retention times. By controlling the column temperature and other conditions, compounds with different boiling points can be separated in order.

[0067] The weak polar column as a two-dimensional chromatographic column further classifies the remaining compounds based on polarity on the basis of preliminary separation. Polar molecules have longer retention times on polar columns, while non-polar molecules have shorter retention times. This difference allows naphthenes with similar structures but slightly different polarities to form unique distribution patterns in two-dimensional chromatograms, facilitating the identification of target compounds in subsequent steps.

[0068] Specifically, 1.5 mL of coal direct liquefaction oil A is taken in a chromatographic flask, and the full two-dimensional gas chromatography conditions are set as follows: the injection amount is 0.2 μL, the injection port temperature is 300 ℃, the column flow rate is 1.0 mL / min, and the chromatographic program temperature rising conditions are as follows: The mass spectrometry conditions are set as follows: ion source temperature is 250 DEG C, solvent delay is 60 s, and collection frequency is 100 spec / s; hydrogen flame ionization detector conditions are as follows: solvent is not delayed, detector temperature is 320 DEG C, collection speed is 100 spectra / s, tail gas He is used, flow rate is 50 mL / min, air flow rate is 450 mL / min, and hydrogen flow rate is 40 mL / min.

[0069] The full two-dimensional spectrum of the monocyclic hydrocarbon after qualitative determination is obtained by using the above method, and is shown in Figure 4 The full two-dimensional distribution diagram of the monocyclic hydrocarbon in the coal direct liquefaction oil on the hydrogen flame ionization detector is obtained by using the above method, and is shown in Figure 5 (part of data), and the distribution data are shown in Table 1. Table 1 only shows part of the distribution data of the monocyclic hydrocarbon on the hydrogen flame ionization detector in the coal direct liquefaction oil A.

[0070] Table 1

[0071]

[0072]

[0073] Specifically, the purpose of the scheme is to provide a method for rapidly determining the qualitative and quantitative monocyclic hydrocarbon in the coal direct liquefaction oil. According to the "special" peak position of the monocyclic hydrocarbon on the full two-dimensional, the "direct observation method" and the "Excel screening method according to the peak rule" are introduced to rapidly determine the peak of the monocyclic hydrocarbon, find the corresponding peak area, and then determine the quantitative area by the area normalization method. The method provides a reference for detailed characterization of the composition of the coal direct liquefaction oil.

[0074] Specifically, the data collected by the hydrogen flame ionization detector is used for screening the monocyclic hydrocarbon, including the monocyclic hydrocarbon and the monocyclic hydrocarbon. There are two methods for screening the monocyclic hydrocarbon, one is the direct observation method, and the other is the Excel screening method according to the peak rule. The following will be introduced respectively.

[0075] In the implementation process, the target compound in the separated compounds can be determined according to the one-dimensional retention time and the two-dimensional retention time of each compound. The target compound can be determined by the following steps: determining the compound with the largest one-dimensional retention time as the first candidate compound, determining the compound with the largest one-dimensional retention time among the compounds other than the first candidate compound as the second candidate compound; in the case that the two-dimensional retention time of the first candidate compound is greater than the two-dimensional retention time of the second candidate compound, determining the first candidate compound as the cyclohexane and the second candidate compound as the cyclopentane; in the case that the two-dimensional retention time of the first candidate compound is less than the two-dimensional retention time of the second candidate compound, determining the second candidate compound as the cyclohexane and the first candidate compound as the cyclopentane.

[0076] In the scheme, in the full two-dimensional spectrum, the retention time of the n-alkyl substituted cycloalkane follows the “tile effect”, and the compound with the largest retention time is usually the target compound. By comparing the two-dimensional retention times of the two compounds with the largest one-dimensional retention time, it can be determined which is the cyclohexane and which is the cyclopentane. The polarity difference between cyclohexane and cyclopentane will cause a difference in their retention time on the two-dimensional chromatographic column. By comparing the two-dimensional retention times, the target compound can be further accurately determined.

[0077] In some embodiments, the compound with the largest one-dimensional retention time is determined as the first candidate compound, and the compound with the largest one-dimensional retention time among the compounds other than the first candidate compound is determined as the second candidate compound. The first candidate compound and the second candidate compound can be determined by the following steps: sorting the plurality of one-dimensional retention times in descending order to obtain a plurality of sorted one-dimensional retention times; extracting the first two one-dimensional retention times from the plurality of sorted one-dimensional retention times; calculating the difference between the first two one-dimensional retention times to obtain a retention time difference; in the case that the retention time difference is less than or equal to a preset time threshold, determining the compound with the largest one-dimensional retention time among the first two one-dimensional retention times as the first candidate compound, and determining the other compound among the first two one-dimensional retention times as the second candidate compound.

[0078] In the scheme, by arranging the compounds according to one-dimensional retention time, the compound with the longest retention time can be quickly located. After sorting, the first two can be directly selected, without the need for detailed analysis of the entire data set. If the retention times of the two compounds are very close, the two compounds are in the upper right corner of the tile and are paired, that is, the distance is close. By comparing the two-dimensional retention times of the two compounds with the longest one-dimensional retention time, it is determined which is cyclohexane and which is cyclopentane. The polarity difference between cyclohexane and cyclopentane will cause a difference in their retention times on the two-dimensional chromatographic column. By the size of the two-dimensional retention time, the target compound can be further accurately determined.

[0079] Specifically, a preset time threshold is set, for example, 0.2 min (or any other reasonable value), to determine whether the two compounds with the longest retention time can be clearly distinguished, that is, the two compounds are close in distance on the two-dimensional chromatogram.

[0080] Specifically, the method described above for determining the normal substituted cyclohexane and the normal substituted cyclopentane is to classify a cycloalkane into C5-C n H 2n , C6-C n H 2n , C7-C n H 2n , C8-C n H 2n ……, and in each category, find: ① the two peaks with the longest time in one-dimensional retention time, ② located in the upper right corner of the tile of the family, ③ the two compounds appear in pairs, and determine the normal substituted cyclohexane and the normal substituted cyclopentane according to the three conditions.

[0081] The peak appearance rule of the compound on the full two-dimensional follows that the peak appears according to the boiling point in one-dimensional retention time, and the peak appears according to the polarity in two-dimensional retention time. Within the family of cycloalkanes, the normal substituted cyclohexane and the normal substituted cyclopentane in the same molecular formula are hydrocarbon fingerprint compounds in the refining process. They have the largest boiling point and the highest polarity.

[0082] Specifically, the method for determining the normal substituted cyclohexane and the normal substituted cyclopentane is to compare the two-dimensional retention times of the two peaks after determining the normal substituted cyclohexane and the normal substituted cyclopentane pair of peaks, wherein the normal substituted cyclohexane has a larger two-dimensional retention time, and the normal substituted cyclopentane has a smaller two-dimensional retention time.

[0083] The one-dimensional retention time is the retention time of a compound on a first-dimensional chromatographic column, reflecting its retention behavior in a first-dimensional separation mechanism (usually a non-polar column based on boiling point difference). The two-dimensional retention time is the retention time of a compound on a second-dimensional chromatographic column, reflecting its retention behavior in a second-dimensional separation mechanism (usually a polar column based on polarity). The one-dimensional retention time is usually based on boiling point / volatility, and the two-dimensional retention time is usually based on polarity / interaction force. In full two-dimensional gas chromatography, the two-dimensional retention time is constrained by the one-dimensional flow-out time and the modulation period.

[0084] The peak-out rule of compounds in full two-dimensional is that, in the one-dimensional retention time, the peak-out is based on boiling point, and in the two-dimensional retention time, the peak-out is based on polarity. Within the family of naphthenes, the n-alkyl substituted cyclohexanes and n-alkyl substituted cyclopentanes in the same molecular formula are hydrocarbon fingerprint compounds in the refining process, which have the highest boiling point and the highest polarity.

[0085] In the implementation process, after calculating the difference between the first two one-dimensional retention times in the sorted plurality of one-dimensional retention times, obtaining the retention time difference, the method further includes the following steps: in the case that the retention time difference is greater than the preset time threshold, extracting the largest one-dimensional retention time in the sorted plurality of one-dimensional retention times, obtaining the peak one-dimensional retention time; determining the compound corresponding to the peak one-dimensional retention time as the cyclohexane, and determining the content of the cyclopentane as 0.

[0086] In the scheme, in the actual analysis scene, the retention time difference may be too large, which indicates that the second candidate compound may not be cyclopentane, but another completely different compound, that is, the two compounds are far apart in the two-dimensional chromatogram, and are not paired, in this case, continuing to try to identify the second compound may consume more time and the result is not accurate, therefore, the compound with the largest retention time is directly determined as the cyclohexane, and the possible cyclopentane is ignored, to ensure the rapidity of analysis and the reliability of target compound identification.

[0087] Specifically, in the method for determining n-alkyl substituted cyclohexanes and n-alkyl substituted cyclopentanes, the "③ two compounds appearing in pairs" must be combined, if only one appears in the chromatogram, the peak is n-alkyl substituted cyclohexane, and there is no n-alkyl substituted cyclopentane.

[0088] Specifically, to determine the n-alkyl substituted naphthene, the n-alkyl substituted cyclopentane and the n-alkyl substituted cyclohexane are quickly determined. It is observed that Figure 5 The compounds (C5, C6, C7, C8, …, in turn, represent the family of C5-C n H 2n , C6-C n H 2nC7-C n H 2n C8-C n H 2n C9-C Figure 5 The peak areas of the normal-substituted cyclohexane and the normal-substituted cyclopentane are determined in the obtained Excel data table as in the above "Table 1", see Table 2, which shows the normal-substituted cyclohexane and the normal-substituted cyclopentane determined in the coal direct liquefaction oil A. Figure 6 Figure 6 The peak areas of the normal-substituted cyclohexane and the normal-substituted cyclopentane are determined in the obtained Excel data table as in the above "Table 1", see Table 2, which shows the normal-substituted cyclohexane and the normal-substituted cyclopentane determined in the coal direct liquefaction oil A.

[0089] Table 2

[0090]

[0091]

[0092] The normal-substituted monocycloalkane standard sample is analyzed by the above-mentioned full two-dimensional gas chromatography method for analyzing the coal direct liquefaction oil A, and the qualitative results are determined, and the obtained full two-dimensional distribution diagram of the normal-substituted monocycloalkane standard sample on the hydrogen flame ionization detector is shown in Figure 7 , and the distribution data is shown in Table 3, which shows the distribution data of the normal-substituted monocycloalkane standard sample on the hydrogen flame ionization detector, wherein "R.T. (s) (1)" is the peak time of the monocycloalkane standard sample on the hydrogen flame ionization detector, and "R.T. (s) (2)" is the peak time of the corresponding normal-substituted cycloalkane determined in the coal direct liquefaction oil A.

[0093] Table 3

[0094] Peak# Name R.T.(s)(1) R.T.(s)(2) 1 Cyclopentane 420,0.950 420,0.930 2 Methylcyclopentane 528,1.050 528,1.020 3 Ethylcyclopentane 774,1.280 / 4 Methylcyclohexane 810,1.290 810,1.250 5 Ethylcyclohexane 1194,1.530 1194,1.480 6 Propylcyclohexane 1626,1.660 1626,1.580 7 Butylcyclohexane 2106,1.680 2106,1.620 8 Heptylcyclohexane 3458,1.790 3466,1.710 9 N-octylcyclohexane 3866,1.830 3866,1.760 10 Tridecylcyclohexane 5570,2.030 5570,1.920

[0095] In some embodiments, after determining the target compound in the separated compound according to the one-dimensional retention time and the two-dimensional retention time of the separated compound, the method further comprises the steps of: calculating the mass fraction of the compound according to a target formula, and sending the mass fraction to the target device to guide the target object to improve the catalyst, wherein the target formula is:

[0096] ωi represents the mass fraction, mi represents the mass of the i-th compound, m represents the total mass of all the compounds, and n represents the number of the compounds. i

[0097] In this scheme, the quantitative analysis process of the compound is simplified by area normalization method, the influence of the correction factor is ignored, the calculation is simplified, and thus the calculation speed of the mass fraction is accelerated.​​

[0098] Specifically, the data collected by the hydrogen flame ionization detector are quantitatively used, and one of the two methods for determining the normal-substituted cyclohexanes and normal-substituted cyclopentanes is used to find the peak area corresponding to the normal-substituted cycloalkanes in the Excel data table.

[0099] The quantitative analysis used data collected by a hydrogen flame ionization detector. The quantitative analysis method for n-substituted cyclohexane and n-substituted cyclopentane was the area normalization method. The influence of the correction factor was ignored. The calculation formula was the same as the target formula mentioned above. Of course, the target formula can also be expressed as:

[0100]

[0101] f i Indicates the correction factor. There are two methods for correction factor: one is to look it up in reference books, and the other is to calculate it using standard products. The formula is f m =(A s ×m i ) / (A i ×m s ). A s is the area of ​​the standard, m s It is the quality of the standard product.

[0102] Assume that there are n components in the sample, and the mass of each component is m1, m2, ···, m n , the sum of the contents of each component is m, where the mass fraction of the i-th component is ω i , f i is the mass correction factor of the i-th component.

[0103] In one application example, a control device sends the calculated mass fraction information to the catalyst preparation system to quickly adjust the catalyst formulation. Specifically, if the cyclohexane mass fraction is found to be lower than expected (for example, the target is 15%), the loading of a specific metal can be automatically increased to promote cyclohexane production. Conversely, if the cyclopentane mass fraction is too high, measures can be taken to reduce its production, such as adjusting the reaction temperature or pressure conditions. Through this method, companies can instantly optimize catalyst performance, improve the processing efficiency and finished oil quality of coal liquefaction products, and reduce production costs caused by poor catalyst performance.

[0104] In the implementation process, after obtaining the one-dimensional retention time of each compound in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each compound in the two-dimensional chromatographic column, the method further comprises the following steps: constructing a table and displaying the table in a display interface, wherein the table comprises at least a first column and a second column, the data in the first column is the one-dimensional retention time, and the data in the second column is the two-dimensional retention time; detecting and responding to a first operation to sort the one-dimensional retention time in the first column in descending or ascending order, wherein the first operation is used to sort the data in the first column; detecting and responding to a second operation to sort the two-dimensional retention time in the second column in descending or ascending order, wherein the second operation is used to sort the data in the second column; and displaying the sorted table in the display interface.

[0105] In this scheme, the one-dimensional and two-dimensional retention times are displayed in a table, which intuitively presents the separation characteristics of the compounds. The sorting function enables the experimenter to quickly focus on the compound with the longest or shortest retention time, which can intuitively display the difference in retention time of various compounds.

[0106] Specifically, the experimenter's sorting operation on the display interface is detected, for example, clicking the sorting icon on the right side of the “one-dimensional retention time” column title. According to the experimenter's sorting instruction, the one-dimensional retention time data in the first column is sorted, which can be from large to small or from small to large.

[0107] Specifically, the experimenter's sorting request for the two-dimensional retention time is detected, for example, by clicking the sorting button of the “two-dimensional retention time” column. The two-dimensional retention time data in the second column is sorted, and ascending or descending arrangement is also supported.

[0108] Specifically, the data collected by the hydrogen flame ionization detector is quantified, and the obtained naphthene distribution data on the hydrogen flame ionization detector is filtered out and copied into Excel. The Excel data table contains “peak” column, “Group” column, “R.T. (s)” column and “Area” column.

[0109] The method for determining normal substituted cyclohexane and normal substituted cyclopentane according to the peak emergence rule Excel filtering method is to set the filtering function of the “Group” column in the obtained Excel data table.

[0110] In the method for determining normal-substituted cyclohexane and normal-substituted cyclopentane according to the peak appearance rule Excel screening method, C5-CnH2n, C6-CnH2n, C7-CnH2n, C8-CnH2n…… are screened out according to the "Group" column, and the compounds in each group are sorted according to one-dimensional retention time, and the two peaks with the largest one-dimensional retention time are determined as normal-substituted cyclohexane and normal-substituted cyclopentane.

[0111] In the method for determining normal-substituted cyclohexane and normal-substituted cyclopentane according to the peak appearance rule Excel screening method, after a pair of normal-substituted cyclohexane and normal-substituted cyclopentane is determined, the two-dimensional retention times of the two peaks are compared, and the one with the larger two-dimensional retention time is normal-substituted cyclohexane, and the one with the smaller two-dimensional retention time is normal-substituted cyclopentane.

[0112] Specifically, normal-substituted cycloalkanes, normal-substituted cyclopentane and normal-substituted cyclohexane are quickly determined according to the peak appearance rule Excel screening method.

[0113] By using the above method, the "Group" column in "Table 1" is set to have a screening function, and C5-C n H 2n , C6-C n H 2n , C7-C n H 2n , C8-C n H 2n …… are screened out in turn, and then each group screened out is sorted according to one-dimensional retention time, and the one with the largest one-dimensional retention time is determined as normal-substituted cyclohexane in the group, and the one with the second largest one-dimensional retention time is determined as normal-substituted cyclopentane in the group. The determined compounds are the same as "Table 2".

[0114] The peak appearance time "R.T. (s) (1)" of the cycloalkane standard in Table 3 on the hydrogen flame ionization detector is compared with the peak appearance time "R.T. (s) (2)" of the corresponding normal-substituted cycloalkane determined in the coal direct liquefaction oil A, and it is determined that the two methods for determining normal-substituted cyclohexane and normal-substituted cyclopentane are correct.

[0115] In some embodiments, after the one-dimensional retention time of each of the above compounds in the above one-dimensional chromatographic column and the two-dimensional retention time of each of the above compounds in the above two-dimensional chromatographic column are obtained, the method further includes the following steps: deleting the data that is empty in the plurality of one-dimensional retention times; and deleting the data that is empty in the plurality of two-dimensional retention times.

[0116] In this scheme, by removing invalid one-dimensional retention time and two-dimensional retention time, i.e. removing empty values, the data can be made more pure, and the effectiveness of the data is better.

[0117] In summary, the method for rapidly determining n-substituted monocyclic alkanes in coal direct liquefaction oil provided by the scheme of the application uses full two-dimensional gas chromatography-time-of-flight mass spectrometry / hydrogen flame ionization detector to analyze coal direct liquefaction oil, uses time-of-flight mass spectrometry detection data for qualitative analysis, and uses hydrogen flame ionization detector detection data for quantitative analysis, quickly determines n-substituted cyclohexane and n-substituted cyclopentane according to the "special" peak position of n-substituted monocyclic alkanes in full two dimensions, and then uses the area normalization method for quantitative analysis. The method has good separation effect, can separate n-substituted cyclohexane and n-substituted cyclopentane from other monocyclic alkanes with the same carbon number or adjacent carbon number, is fast and convenient for qualitative and quantitative analysis, does not require any pretreatment of the oil sample, introduces two methods for quickly determining n-substituted cyclohexane and n-substituted cyclopentane, greatly saves the time of analysts, and improves the analysis efficiency; the method has high accuracy and reduces the probability of misjudgment.

[0118] The control device of the naphthene detection system provided in the embodiments of the application can be used to execute the separation method for naphthene provided in the embodiments of the application. The device is used to implement the above embodiments and preferred embodiments, and will not be described again. As used below, the term "module" can be a combination of software and / or hardware that implements a predetermined function. Although the device described in the following embodiments is preferably implemented in software, implementation in hardware or a combination of software and hardware is also possible and contemplated. The naphthene detection system described above includes a control device and a detection device. The control device is used to control the detection device to separate compounds. The detection device includes at least a one-dimensional chromatographic column and a two-dimensional chromatographic column. The one-dimensional chromatographic column is used to separate multiple compounds according to the difference in boiling point of the compounds. The two-dimensional chromatographic column is used to separate multiple compounds that cannot be separated by the one-dimensional chromatographic column according to the difference in polarity of the compounds.

[0119] The control device of the naphthene detection system provided in the embodiments of the application is described below.

[0120] Figure 8 is a structural block diagram of the control device of the naphthene detection system according to the embodiments of the application. As shown in Figure 8 , the device includes:

[0121] The first acquisition unit 100 is used to control the detection device to separate the compounds, acquire the one-dimensional retention time of each compound in the one-dimensional chromatographic column, and acquire the two-dimensional retention time of each compound in the two-dimensional chromatographic column. The one-dimensional retention time is the time required for the one-dimensional chromatographic column to separate the compounds. The two-dimensional retention time is the time required for the two-dimensional chromatographic column to separate the compounds.

[0122] The first determining unit 200 is configured to determine a target compound from the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane.

[0123] The processing unit 300 is configured to obtain the content of the target compound and send the content to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve the catalyst.

[0124] In this embodiment, two chromatographic columns of the detection device are used to separate sample compounds. The one-dimensional chromatographic column preliminarily separates compounds based on the boiling point difference of the compounds. Compounds with different boiling points will leave the one-dimensional column at different time points. This time is referred to as one-dimensional retention time. Subsequently, the compounds preliminarily separated by the one-dimensional column are introduced into the two-dimensional column. The two-dimensional column separates the compounds again according to the polarity difference of the compounds. Compounds with different polarities have different retention times on the two-dimensional column. This time is referred to as two-dimensional retention time. The boiling point of cyclohexane and cyclopentane is very high, and the polarity is also very high. Therefore, cyclohexane and cyclopentane can be quickly screened out through the two retention times. Therefore, compared with the traditional large-scale experiment for measurement, the separation function of the detection device is combined with the characteristics of cyclohexane and cyclopentane to quickly screen and measure. Compared with the prior art, the measurement speed is faster.

[0125] In the implementation process, the first determining unit includes a first determining module, a second determining module, and a third determining module. The first determining module is configured to determine a compound with the largest one-dimensional retention time as a first candidate compound. Among the compounds other than the first candidate compound, a compound with the largest one-dimensional retention time is determined as a second candidate compound. The second determining module is configured to determine the first candidate compound as the cyclohexane and the second candidate compound as the cyclopentane when the two-dimensional retention time of the first candidate compound is greater than the two-dimensional retention time of the second candidate compound. The third determining module is configured to determine the second candidate compound as the cyclohexane and the first candidate compound as the cyclopentane when the two-dimensional retention time of the first candidate compound is less than the two-dimensional retention time of the second candidate compound.

[0126] In the scheme, in the full two-dimensional spectrum, the retention time of the normal substituted cycloalkane follows the "tile effect", and the compound with the maximum retention time is usually the target compound. By comparing the two-dimensional retention times of the compounds with the two maximum one-dimensional retention times, it is determined which is cyclohexane and which is cyclopentane. The polarity difference between cyclohexane and cyclopentane will cause the retention time of the two compounds on the two-dimensional chromatographic column to be different, and the size of the two-dimensional retention time can be used to further accurately determine the target compound.

[0127] In some embodiments, the first determining module includes a sorting submodule, an extracting submodule, a calculating submodule, and a determining submodule. The sorting submodule is configured to sort the plurality of one-dimensional retention times in descending order to obtain a plurality of sorted one-dimensional retention times. The extracting submodule is configured to extract the first two one-dimensional retention times from the plurality of sorted one-dimensional retention times. The calculating submodule is configured to calculate the difference between the first two one-dimensional retention times to obtain a retention time difference. The determining submodule is configured to, in the case that the retention time difference is less than or equal to a preset time threshold, determine the compound with the maximum one-dimensional retention time from the first two one-dimensional retention times as the first candidate compound, and determine another compound with one-dimensional retention time from the first two one-dimensional retention times as the second candidate compound, except for the first candidate compound.

[0128] In the scheme, by sorting the compounds according to the one-dimensional retention time, the compound with the maximum retention time can be quickly located. The first two compounds are directly selected after sorting, without the need for detailed analysis of the entire data set. If the retention times of the two compounds are very close, the two compounds are located at the upper right corner of the tile and are paired, i.e., close to each other. By comparing the two-dimensional retention times of the compounds with the two maximum one-dimensional retention times, it is determined which is cyclohexane and which is cyclopentane. The polarity difference between cyclohexane and cyclopentane will cause the retention time of the two compounds on the two-dimensional chromatographic column to be different, and the size of the two-dimensional retention time can be used to further accurately determine the target compound.

[0129] In the specific implementation process, the apparatus further includes a second obtaining unit and a second determining unit. The second obtaining unit is configured to, after calculating the difference between the first two one-dimensional retention times from the plurality of sorted one-dimensional retention times to obtain a retention time difference, extract the one-dimensional retention time with the maximum one-dimensional retention time from the plurality of sorted one-dimensional retention times to obtain a peak one-dimensional retention time, in the case that the retention time difference is greater than the preset time threshold. The second determining unit is configured to determine the compound corresponding to the peak one-dimensional retention time as the cyclohexane, and determine the content of the cyclopentane as 0.

[0130] In the scheme, in the actual analysis scene, a situation that the retention time difference is too large can be encountered, which indicates that the second candidate compound can not be cyclopentane, but another completely different compound, that is, the two compounds are far away in the two-dimensional chromatogram and are not paired, in this case, continuing to try to identify the second compound can consume more time and the result is inaccurate, therefore, the compound with the largest retention time is directly determined as cyclohexane, and the possible cyclopentane is ignored, so as to ensure the rapidity of analysis and the reliability of target compound identification.

[0131] In some embodiments, the device further comprises a calculation unit configured to, after determining the target compound from the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, calculate the mass fraction of the compound according to a target formula, and send the mass fraction to the target device to guide the target object to improve the catalyst, wherein the target formula is:

[0132] ωi represents the mass fraction, m i represents the mass of the i th compound, m represents the total mass of all the compounds, and n represents the number of the compounds.

[0133] In the scheme, the area normalization method is used to simplify the quantitative analysis process of the compounds, the influence of the correction factor is ignored, the calculation is simplified, and thus the calculation speed of the mass fraction is accelerated.

[0134] In the specific implementation process, the unit includes a first display unit, a first response unit, a second response unit, and a second display unit. The first display unit is configured to, after obtaining the one-dimensional retention time of each compound in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each compound in the two-dimensional chromatographic column, construct a table and display the table in a display interface, wherein the table includes at least a first column and a second column, the data in the first column is the one-dimensional retention time, and the data in the second column is the two-dimensional retention time. The first response unit is configured to detect and respond to a first operation to sort the one-dimensional retention time in the first column in descending or ascending order, wherein the first operation is used to sort the data in the first column. The second response unit is configured to detect and respond to a second operation to sort the two-dimensional retention time in the second column in descending or ascending order, wherein the second operation is used to sort the data in the second column. The second display unit is configured to display the sorted table in the display interface.

[0135] In the scheme, one-dimensional and two-dimensional retention times are displayed through a table, and separation characteristics of the compounds are intuitively presented, and the sorting function enables the experimenter to quickly focus on the compounds with the longest or shortest retention time, so that the differences in the retention times of various compounds can be intuitively displayed.

[0136] In some embodiments, the device further comprises a first deletion unit and a second deletion unit, the first deletion unit is configured to delete data that is empty in the plurality of one-dimensional retention times after obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, and the second deletion unit is configured to delete data that is empty in the plurality of two-dimensional retention times.

[0137] In the scheme, by removing invalid one-dimensional retention times and two-dimensional retention times, i.e., removing empty values, the data can be more pure, and the effectiveness of the data is better.

[0138] The control device of the naphthene detection system comprises a processor and a memory, the first acquisition unit, the first determination unit, and the processing unit are stored in the memory as program units, and the corresponding functions are realized by the processor executing the program units stored in the memory. The modules are located in the same processor, or the modules are located in different processors in any combination.

[0139] The processor comprises a core, and the core retrieves the corresponding program unit from the memory. The core can be set to one or more, and the problem that the naphthene (cyclohexane or cyclopentane) cannot be quickly measured in the prior art can be solved by adjusting the core parameters.

[0140] The memory can include non-permanent memory in a computer readable medium, random access memory (RAM), and / or non-volatile memory such as read-only memory (ROM) or flash memory (flash RAM), and the memory comprises at least one memory chip.

[0141] The embodiment of the present application provides a computer readable storage medium, and the computer readable storage medium comprises a stored program, wherein the computer readable storage medium controls a device in which the computer readable storage medium is located to execute the separation method of the naphthene when the program runs.

[0142] The embodiment of the present application provides a processor, and the processor is used for running a program, wherein the separation method of the naphthene is executed when the program runs.

[0143] The embodiment of the present application provides a device, the device comprises a processor, a memory and a program stored on the memory and executable on the processor, and the processor implements at least a separation step of naphthenes when executing the program. The device herein can be a server, a PC, a PAD, a mobile phone and the like.

[0144] The present application also provides a computer program product adapted to execute a program for initializing at least a separation step of naphthenes when executed on a data processing device.

[0145] The present application also provides a naphthene detection system, comprising a control device and a detection device, the control device is used for controlling the detection device to separate compounds, the detection device comprises at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column is used for separating a plurality of compounds according to different boiling points of the compounds, the two-dimensional chromatographic column is used for separating a plurality of compounds which cannot be separated by the one-dimensional chromatographic column according to different polarities of the compounds, and the control device is used for executing steps of any one of the separation methods of naphthenes.

[0146] Obviously, those skilled in the art should understand that each module or step of the present application described above can be realized by a general computing device, which can be centralized on a single computing device or distributed on a network composed of multiple computing devices, and can be realized by program codes executable by the computing device, so that they can be stored in a storage device and executed by the computing device, and in some cases, the steps shown or described herein can be executed in different order, or they can be respectively manufactured into each integrated circuit module, or multiple modules or steps thereof can be manufactured into a single integrated circuit module. Therefore, the present application is not limited to any specific combination of hardware and software.

[0147] Those skilled in the art should understand that the embodiments of the present application can be provided as a method, a system or a computer program product. Therefore, the present application can be in the form of a complete hardware embodiment, a complete software embodiment or an embodiment combining software and hardware aspects. Moreover, the present application can be in the form of a computer program product implemented on one or more computer usable storage media (including but not limited to magnetic disk storage, CD-ROM, optical storage and the like) containing computer usable program codes.

[0148] The computer program instructions can also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer-implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart block or blocks. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof.

[0149] The computer program instructions can also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer-implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart block or blocks. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof.

[0150] The computer program instructions can also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer-implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart block or blocks. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof. Figure 1 one or more flowcharts and / or blocks in the flowcharts and / or combination thereof.

[0151] In one typical configuration, the computing device includes one or more processors (CPUs), input / output interfaces, network interfaces, and memory.

[0152] The memory can include non-persistent memory and / or volatile memory, such as a random access memory (RAM) including a cache area for the temporary storage of data. The memory can also include non-volatile memory, such as read only memory (ROM) for storing structural information and / or instruction code to boot an operating system. The memory can include flash memory. The memory can include one or more memories, or classes of memory, each of which can be of one or more types. The memory is an example of computer-readable media.

[0153] Computer-readable media includes permanent and non-permanent, movable and non-movable media that can be implemented by any method or technology to store information. The information can be computer-readable instructions, data structures, program modules or other data. Examples of computer storage media include, but are not limited to, phase-change memory (PRAM), static random access memory (SRAM), dynamic random access memory (DRAM), other types of random access memory (RAM), read-only memory (ROM), electrically erasable programmable read-only memory (EEPROM), flash memory or other memory technology, compact disc read-only memory (CD-ROM), digital versatile disc (DVD) or other optical storage, magnetic cassette, magnetic disk storage or other magnetic storage device, or any other non-transmission medium that can be used to store information accessible to a computing device. According to the definition herein, computer-readable media does not include transitory media such as modulated data signals and carriers.

[0154] The technical features of the above embodiments can be combined in any manner. In order to make the description concise, not all possible combinations of the technical features in the above embodiments are described, however, as long as the combinations of the technical features do not contradict, they should be considered within the scope of the present disclosure.

[0155] It should also be noted that the terms "comprising", "including", or any other variant thereof are intended to cover non-exclusive inclusion, so that processes, methods, articles or devices including a series of elements not only include those elements, but also include other elements not explicitly listed, or inherent to such processes, methods, articles or devices. Without more limitations, the element defined by the statement "comprising a" does not exclude the presence of additional identical elements in the process, method, article or device including the element.

[0156] The above description is only preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for separating cycloalkanes, characterized in that: The method is applied to a cycloalkane detection system, which includes a control device and a detection device. The control device is used to control the detection device to separate compounds. The detection device includes at least a one-dimensional chromatographic column and a two-dimensional chromatographic column. The one-dimensional chromatographic column is used to separate multiple compounds according to different boiling points of the compounds. The two-dimensional chromatographic column is used to separate multiple compounds that cannot be separated by the one-dimensional chromatographic column according to different polarities of the compounds. The method includes: Controlling the detection device to separate the compounds, obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column, and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, wherein the one-dimensional retention time is the time required for the one-dimensional chromatographic column to separate the compounds, and the two-dimensional retention time is the time required for the two-dimensional chromatographic column to separate the compounds; Determining a target compound among the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane; The content of the target compound is obtained and sent to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve the catalyst.

2. The method according to claim 1, characterized in that Determining a target compound among the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds comprises: Determine the compound with the longest one-dimensional retention time as a first candidate compound, and among the compounds other than the first candidate compound, determine the compound with the longest one-dimensional retention time as a second candidate compound; When the two-dimensional retention time of the first candidate compound is greater than the two-dimensional retention time of the second candidate compound, the first candidate compound is determined to be the cyclohexane, and the second candidate compound is determined to be the cyclopentane; When the two-dimensional retention time of the first candidate compound is smaller than the two-dimensional retention time of the second candidate compound, the second candidate compound is determined to be the cyclohexane, and the first candidate compound is determined to be the cyclopentane.

3. The method according to claim 2, characterized in that The compound with the largest one-dimensional retention time is determined as the first candidate compound, and among the compounds other than the first candidate compound, Determining the compound with the largest one-dimensional retention time as the second candidate compound comprises: sorting the plurality of one-dimensional retention times in descending order to obtain a plurality of sorted one-dimensional retention times; extracting the first two one-dimensional retention times from the sorted plurality of one-dimensional retention times; Calculating the difference between the first two one-dimensional retention times of the sorted plurality of one-dimensional retention times to obtain a retention time difference; When the retention time difference is less than or equal to a preset time threshold, the compound with the largest one-dimensional retention time among the first two is determined as the first candidate compound, and among the compounds other than the first candidate compound, the other one of the first two one-dimensional retention times is determined as the second candidate compound.

4. The method according to claim 3, characterized in that After calculating the difference between the first two one-dimensional retention times of the sorted plurality of one-dimensional retention times to obtain the retention time difference, the method further includes: When the retention time difference is greater than the preset time threshold, extracting the largest one-dimensional retention time from the sorted multiple one-dimensional retention times to obtain the peak one-dimensional retention time; The compound corresponding to the one-dimensional retention time of the peak is determined to be the cyclohexane, and the content of the cyclopentane is determined to be 0.

5. The method according to claim 1, wherein After determining the target compound among the separated compounds based on the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, the method further includes: According to a target formula, the mass fraction of the compound is calculated and the mass fraction is sent to the target device to guide the target object to improve the catalyst, wherein the target formula is: ωi represents the mass fraction, m i represents the mass of the i-th compound, m represents the total mass of all the compounds, and n represents the number of the compounds.

6. The method according to any one of claims 1 to 5, characterized in that After obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, the method further includes: Constructing a table and displaying the table on a display interface, wherein the table includes at least a first column and a second column, the data in the first column is the one-dimensional retention time, and the data in the second column is the two-dimensional retention time; detecting and responding to a first operation, sorting the one-dimensional retention times of the first column in a descending order or a descending order, wherein the first operation is used to sort the data of the first column; detecting and responding to a second operation, sorting the two-dimensional retention times of the second column in order from largest to smallest or from smallest to largest, wherein the second operation is used to sort the data of the second column; The sorted table is displayed on the display interface.

7. The method according to any one of claims 1 to 5, characterized in that After obtaining the one-dimensional retention time of each of the compounds in the one-dimensional chromatographic column and obtaining the two-dimensional retention time of each of the compounds in the two-dimensional chromatographic column, the method further includes: deleting multiple empty data in the one-dimensional retention time; Delete multiple empty data in the two-dimensional retention time.

8. A control device for a cycloalkane detection system, characterized in that: The cycloalkane detection system includes a control device and a detection device, wherein the control device is used to control the detection device to separate compounds, and the detection device includes at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, wherein the one-dimensional chromatographic column is used to separate multiple compounds according to the different boiling points of the compounds, and the two-dimensional chromatographic column is used to separate multiple compounds that cannot be separated by the one-dimensional chromatographic column according to the different polarities of the compounds. The device includes: a first acquisition unit, configured to control the detection device to separate the compounds, acquire the one-dimensional retention time of each compound in the one-dimensional chromatographic column, and acquire the two-dimensional retention time of each compound in the two-dimensional chromatographic column, wherein the one-dimensional retention time is the time required for the one-dimensional chromatographic column to separate the compounds, and the two-dimensional retention time is the time required for the two-dimensional chromatographic column to separate the compounds; a first determining unit, configured to determine a target compound among the separated compounds according to the one-dimensional retention time and the two-dimensional retention time of each of the separated compounds, wherein the target compound is cyclohexane or cyclopentane; A processing unit is used to obtain the content of the target compound and send the content to a target device, wherein the target device is a device used by a target object, so as to guide the target object to improve the catalyst.

9. A computer program product comprising a computer program, characterized in that When the computer program is executed by a processor, the steps of the method for separating cycloalkanes according to any one of claims 1 to 7 are implemented.

10. A cycloalkane detection system, characterized in that: include: A control device and a detection device, wherein the control device is used to control the detection device to separate compounds, and the detection device includes at least a one-dimensional chromatographic column and a two-dimensional chromatographic column, the one-dimensional chromatographic column is used to separate multiple compounds according to the differences in the boiling points of the compounds, and the two-dimensional chromatographic column is used to separate multiple compounds that cannot be separated by the one-dimensional chromatographic column according to the differences in the polarities of the compounds, and the control device is used to perform the steps of the cycloalkane separation method according to any one of claims 1 to 7.

Images