CN113533567A - Typical diene qualitative and quantitative detection method - Google Patents
Typical diene qualitative and quantitative detection method Download PDFInfo
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- CN113533567A CN113533567A CN202110794831.0A CN202110794831A CN113533567A CN 113533567 A CN113533567 A CN 113533567A CN 202110794831 A CN202110794831 A CN 202110794831A CN 113533567 A CN113533567 A CN 113533567A
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
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- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
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- G01N30/02—Column chromatography
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- G01N30/72—Mass spectrometers
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a typical diene qualitative and quantitative detection method, which adopts gas chromatography for quantification, adopts gas chromatography mass spectrometry for qualitative determination, detects seven diene components in gasoline at one time, has the advantages of high speed, high accuracy, good repeatability and the like, obtains good consistency with the traditional method for determining diene value by maleic anhydride addition reaction, and solves a great technical problem of diene detection; the detection time is 94min, the analysis process hardly generates pollution, the instrument analysis is adopted, the dual means of retention time and mass spectrogram similarity are utilized for matching, the human errors are greatly reduced, and compared with the common means of qualitative matching only by utilizing the retention time, the data reliability is greatly increased, the non-dialkene is hardly misread as the dialkene, and the real dialkene is not misread as the non-dialkene; meanwhile, the quantitative result is calculated by adopting the peak area normalization of the hydrogen flame detector, the quantitative result is close to the real result, and the standard addition recovery rate is very ideal.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a typical diene qualitative and quantitative detection method.
Background
For a long time, the content of diolefin in gasoline is a technical problem, and at present, no mature and reliable method for detecting the content of diolefin in gasoline is available. The actual colloid content and the induction period of the gasoline can be influenced by the content of the diolefin in the gasoline, the actual colloid content is increased due to the high content of the diolefin, and the induction period is shortened, so that the product is unqualified.
The methods currently used for detecting diolefins in gasoline are summarized mainly as comprising:
1, UOP 326: measuring a diene value by a maleic anhydride addition reaction method;
2. gas chromatography (GC-FID) is used for measuring the dialkene in the gasoline instead of the maleic anhydride addition method;
3. rapidly measuring the diene value of the pyrolysis gasoline by infrared spectroscopy;
4. and (3) determining the conjugated diene in the oil product by an ultraviolet spectrophotometry.
The method has obvious defects, the testing time is long when the diene value is measured by the maleic anhydride addition reaction method, a plurality of reagents are required for chemical reaction, and the detection cost is high; the gas chromatography (GC-FID) is difficult to determine the alkadiene in the gasoline, and the alkadiene cannot be determined accurately through retention time due to the complex gasoline components; the infrared spectrum rapid determination of the diene value of the pyrolysis gasoline can only be qualitative at present, is difficult to carry out accurate quantification, and has poor accuracy of a detection result; the ultraviolet spectrophotometry method for determining the conjugated diene in the oil product has the trouble of more interference factors.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for qualitatively and quantitatively detecting typical diene by using a gas chromatography.
In order to achieve the purpose and achieve the technical effect, the invention adopts the technical scheme that:
a typical diene qualitative and quantitative detection method comprises the following steps:
1) injecting the two same samples into a gas chromatograph provided with a flame ionization detector and a capillary column and a gas chromatography mass spectrometer provided with a capillary column respectively, simultaneously carrying out sample injection analysis to obtain a gas chromatogram and a gas chromatography mass spectrum respectively, and respectively confirming the retention time and the peak position of each component in the gas chromatograph and the gas chromatography mass spectrometer;
2) analyzing the sample under the same condition, and determining the suspected diene component by using the retention time and the similarity of the gas chromatography mass spectrogram through the gas chromatography mass spectrogram;
3) the gas chromatogram and the gas chromatogram mass spectrogram have high similarity, and after qualitative confirmation, the gas chromatogram directly finds out the diene component which is qualitatively confirmed on the gas chromatogram mass spectrogram by taking the retention time as a reference;
4) the component concentrations are calculated according to the relative percentage of the total adjusting peak area, the concentrations of all the diene components are normalized, and the area percentages of all the diene components are added to obtain the total content of the required typical diene.
Further, the detection conditions of the gas chromatograph are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
A detector: flame ionization detector
Temperature: 250 deg.C
Hydrogen flow rate: 35mL/min
Air flow rate: 300mL/min
Make-up nitrogen flow rate 25mL/min
The sample size was 0.4. mu.L.
Further, the column temperature program of the gas chromatograph comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
Further, the detection conditions of the gas chromatography-mass spectrometer are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
Temperature: 250 deg.C
The sample size was 0.4. mu.L.
Further, the column temperature program of the gas chromatography mass spectrometer comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
Further, the gas chromatograph determines the retention time of the dienes in the sample by gas chromatography as follows:
1, 3-butadiene: 8.84min
2-methyl-1, 3-butadiene: 11.87min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 22.53min
3-methyl-1, 3-pentadiene trans isomer: 23.14min
Trans-1, 4-hexadiene: 17.83min
2, 4-hexadiene cis isomer: 23.41min
2, 4-hexadiene trans isomer: 24.73min
Dicyclopentadiene 66.43 min.
Further, the gas chromatography mass spectrometer determines the retention time of the diene in the sample by the gas chromatography mass spectrometry as follows:
1, 3-butadiene: 6.6min
2-methyl-1, 3-butadiene: 9.0min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 18.9min
3-methyl-1, 3-pentadiene trans isomer: 19.6min
Trans-1, 4-hexadiene: 14.3min
2, 4-hexadiene cis isomer: 19.9min
2, 4-hexadiene trans isomer: 21.1min
Dicyclopentadiene (2), dicyclopentadiene (ii): 61.1 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a typical diene qualitative and quantitative detection method, which combines a gas chromatography (GC-FID) and a gas chromatography mass spectrometry (GC-MS) to realize the qualitative and quantitative determination of typical diene, adopts the gas chromatography (GC-FID) for the quantitative determination, adopts the gas chromatography mass spectrometry (GC-MS) for the qualitative determination, adopts completely same chromatographic analysis conditions, detects seven typical diene components in gasoline at one time, has the advantages of high speed, high accuracy, good repeatability and the like, obtains good consistency with the traditional method for determining diene value by maleic anhydride addition reaction, and solves a great technical problem of diene detection; the whole detection time is 94min, the analysis process hardly generates pollution, the instrument analysis is adopted, the dual means of retention time and mass spectrogram similarity are utilized for matching, the human errors are greatly reduced, and compared with the common means of qualitative matching only by utilizing the retention time, the data reliability is greatly increased, the non-dialkene is hardly misread as the dialkene, and the real dialkene is not misread as the non-dialkene; meanwhile, the quantitative result is calculated by adopting the peak area normalization of the hydrogen flame detector, the quantitative result is close to the real result, and the standard addition recovery rate is very ideal.
Drawings
FIG. 1 is a gas chromatogram of the present invention;
FIG. 2 is a gas chromatography mass spectrum of the present invention.
Detailed Description
The present invention is described in detail below with reference to the attached drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby clearly defining the protection scope of the present invention.
The following presents a simplified summary of one or more aspects in order to provide a basic understanding of such aspects. This summary is not an extensive overview of all contemplated aspects, and is intended to neither identify key or critical elements of all aspects nor delineate the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that is presented later.
A typical qualitative and quantitative determination method for diolefins is to inject the sample to be analyzed into a gas chromatograph (GC-FID) equipped with a Flame Ionization Detector (FID) and a capillary column, measure and adjust the peak areas of the components using the effective carbon number (ECN response factor), the concentration of each component being calculated from the relative percentage of the total adjusted peak area, normalized to 100.00, and at the same time, to inject the sample under the same operating conditions in a gas chromatograph mass spectrometer (GC-MS) equipped with the same capillary column, to qualitatively confirm the above components. It should be noted that cyclopentadiene is condensed into dicyclopentadiene at 177 ℃, and only the sum of the contents of cyclopentadiene and dicyclopentadiene in the sample can be determined because the injection inlet temperature is 220 ℃.
As a more specific embodiment, the invention discloses a typical diene qualitative and quantitative detection method, which specifically comprises the following steps:
1) preparing a gas chromatograph and a gas chromatograph-mass spectrometer, injecting 1, 3-butadiene, 2-methyl-1, 3-butadiene, cyclopentadiene, 3-methyl-1, 3-pentadiene (cis-trans isomer mixture), trans-1, 4-hexadiene, 2, 4-hexadiene (cis-trans isomer mixture) and dicyclopentadiene into the gas chromatograph-mass spectrometer, injecting the mixture into the gas chromatograph-mass spectrometer under the same condition, determining the retention time of each substance in the gas chromatograph-mass spectrometer and the gas chromatograph-mass spectrometer, mixing the substances in methanol to prepare a diene mixture standard, simultaneously carrying out sample injection analysis, and respectively labeling chromatographic peaks and compound names on two devices of the gas chromatograph-mass spectrometer and the gas chromatograph-mass spectrometer, wherein the standard;
2) analyzing the sample under the same condition, firstly finding out the substances suspected to be the dialkene by using retention time through a gas chromatography mass spectrogram, searching an NIST (nickel-in-situ hybridization) spectrum library for the substances suspected to be the dialkene to confirm each substance, and if the retention time is matched with the NIST spectrum library, confirming the substances to be the dialkene;
3) after qualitative confirmation, because the gas chromatogram mass spectrum and the gas chromatogram have high similarity and the gas chromatogram has the reserved time as a reference, the diolefine component which is qualitatively confirmed on the gas chromatogram mass spectrum can be directly found out from the gas chromatogram;
4) and (4) calculating a result: according to the gas chromatography mass spectrogram and the gas chromatogram, the component concentration is calculated according to the relative percentage of the total adjusting peak area, the alkadiene existing in the sample is selected, the area percentage is referred, the normalized data is directly recorded, and the total content of the alkadiene can be obtained by adding the area percentages of all the alkadiene.
The required equipment of the invention is as follows:
gas chromatograph, model GC-7820A, manufactured by Beijing Zhongkehui instruments Inc., equipped with hydrogen flame detector (FID) and integration workstation, and chromatographic column HP-PONA50m × 0.200mm × 0.50 μm.
A gas chromatography mass spectrometer, model GCMS6800, manufactured by Jiangsu Tianrui instruments GmbH, is equipped with a mass spectrometer detector (MS), a vacuum pump and an integration workstation, and a chromatographic column is HP-PONA50m × 0.200mm × 0.50 μm.
The electronic balance used in the invention was a mettler-toledo ME204E precision electronic balance.
The required reagents and consumables of the invention are as follows:
butadiene, dissolving the body: methanol;
2-methyl-1, 3-butadiene, concentration 99%
Cyclopentadiene, concentration 99%
3-methyl-1, 3-pentadiene (cis-trans mixture) at a concentration of 99%
Trans-1, 4-hexadiene at a concentration of 98%
2, 4-hexadiene at a concentration of 95%
Dicyclopentadiene, concentration 97%
The carrier gas is nitrogen, and the minimum purity is 99.999 mol%
The fuel gas is hydrogen, and the minimum purity is 99.999 mol%
The tail gas is blown by nitrogen, and the minimum purity is 99.999mol percent
The flame supporting gas is air, and the total hydrocarbon is less than 0.1ppm
Helium with a minimum purity of 99.999 mol%.
The detection conditions of the gas chromatograph are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
A detector: flame ionization detector
Temperature: 250 deg.C
Hydrogen flow rate: 35mL/min
Air flow rate: 300mL/min
Make-up nitrogen flow rate 25mL/min
Sample size 0.4 μ L;
the column temperature program of the gas chromatograph comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
The detection conditions of the gas chromatography-mass spectrometer are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
Temperature: 250 deg.C
Sample size 0.4 μ L;
the column temperature program of the gas chromatography mass spectrometer comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
The invention discloses a qualitative and quantitative detection method for typical diene, which can be used for qualitative and quantitative detection of typical diene in gasoline, C5, high olefin C5 and naphtha, and can detect typical 7 diene substances in gasoline at one time, wherein the detection methods are respectively shown in the following table 1:
TABLE 1
The retention time of diolefins in a sample is determined by gas chromatography using a gas chromatograph as shown in fig. 1a and 1 b:
1, 3-butadiene: 8.84min
2-methyl-1, 3-butadiene: 11.87min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 22.53min
3-methyl-1, 3-pentadiene trans isomer: 23.14min
Trans-1, 4-hexadiene: 17.83min
2, 4-hexadiene cis isomer: 23.41min
2, 4-hexadiene trans isomer: 24.73min
Dicyclopentadiene 66.43 min.
Gas chromatograph mass spectrometer determination of the residence time of diolefins in a sample by gas chromatograph mass spectrometry as shown in figure 2:
1, 3-butadiene: 6.6min
2-methyl-1, 3-butadiene: 9.0min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 18.9min
3-methyl-1, 3-pentadiene trans isomer: 19.6min
Trans-1, 4-hexadiene: 14.3min
2, 4-hexadiene cis isomer: 19.9min
2, 4-hexadiene trans isomer: 21.1min
Dicyclopentadiene (2), dicyclopentadiene (ii): 61.1 min.
In order to verify the stability and accuracy of the system, 9 times of labeling measurement are carried out to obtain 9 samples which are respectively labeled as sample one, sample two, sample three, sample four, sample five, sample six, sample seven, sample eight and sample nine, the recovery rates of the nine times of labeling are respectively 98.6%, 101.8%, 102.2%, 103.7%, 104.8%, 105.0%, 105.1%, 108.2% and 115.0% from small to large, the average value is 104.9%, the total amount of the labeling is within 1.00% -5.00%, and the accuracy meets the experimental requirements.
The results of the comparison of the diene values determined according to the invention with those determined by the UOP326 maleic anhydride method of the prior art are shown in table 2:
TABLE 2
According to UOP326, the conversion relationship between diene and diene values is:
diene (mass%) value C/253.8
Wherein C is the molecular weight of the diolefin.
The molecular weight of the above diolefins is between 54 and 132, and the theoretical value of the diolefins is 2 to 5 times that of the diolefins.
The parts of the invention not specifically described can be realized by adopting the prior art or the prior products, and are not described in detail herein.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A typical diene qualitative and quantitative detection method is characterized by comprising the following steps:
1) injecting the two same samples into a gas chromatograph provided with a flame ionization detector and a capillary column and a gas chromatography mass spectrometer provided with a capillary column respectively, simultaneously carrying out sample injection analysis to obtain a gas chromatogram and a gas chromatography mass spectrum respectively, and respectively confirming the retention time and the peak position of each component in the gas chromatograph and the gas chromatography mass spectrometer;
2) analyzing the sample under the same condition, and determining the suspected diene component by using the retention time and the similarity of the gas chromatography mass spectrogram through the gas chromatography mass spectrogram;
3) the gas chromatogram and the gas chromatogram mass spectrogram have high similarity, and after qualitative confirmation, the gas chromatogram directly finds out the diene component which is qualitatively confirmed on the gas chromatogram mass spectrogram by taking the retention time as a reference;
4) the component concentrations are calculated according to the relative percentage of the total adjusting peak area, the concentrations of all the diene components are normalized, and the area percentages of all the diene components are added to obtain the total content of the required typical diene.
2. A method for qualitative and quantitative detection of typical diene according to claim 1, characterized in that the detection conditions of the gas chromatograph are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
A detector: flame ionization detector
Temperature: 250 deg.C
Hydrogen flow rate: 35mL/min
Air flow rate: 300mL/min
Make-up nitrogen flow rate 25mL/min
The sample size was 0.4. mu.L.
3. A method for qualitative and quantitative determination of typical diolefins according to claim 2, wherein said column temperature procedure of gas chromatograph comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
4. A method for qualitative and quantitative detection of typical diene according to claim 1, wherein the detection conditions of the gas chromatograph mass spectrometer are set as follows:
carrier gas: nitrogen gas
Column head pressure: 13.3psi
Mode (2): constant pressure mode
The split ratio is as follows: 100:1
Sample inlet temperature: 220 deg.C
Temperature: 250 deg.C
The sample size was 0.4. mu.L.
5. A method as claimed in claim 4, wherein the column temperature procedure of the gas chromatograph mass spectrometer comprises:
initial temperature: 35 deg.C
Starting time: 15min
Temperature rise rate: 2 ℃/min
Final temperature: 200 deg.C
Final time: and 0 min.
6. A method for qualitative and quantitative determination of typical diolefins according to claim 1, wherein said gas chromatograph determines the retention time of diolefins in the sample by gas chromatography as follows:
1, 3-butadiene: 8.84min
2-methyl-1, 3-butadiene: 11.87min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 22.53min
3-methyl-1, 3-pentadiene trans isomer: 23.14min
Trans-1, 4-hexadiene: 17.83min
2, 4-hexadiene cis isomer: 23.41min
2, 4-hexadiene trans isomer: 24.73min
Dicyclopentadiene 66.43 min.
7. A typical diene qualitative and quantitative detection method as claimed in claim 1, wherein the gas chromatography mass spectrometer determines diene retention time in the sample by gas chromatography mass spectrometry as follows:
1, 3-butadiene: 6.6min
2-methyl-1, 3-butadiene: 9.0min
Cyclopentadiene: polymerization to produce dicyclopentadiene
3-methyl-1, 3-pentadiene cis-isomer: 18.9min
3-methyl-1, 3-pentadiene trans isomer: 19.6min
Trans-1, 4-hexadiene: 14.3min
2, 4-hexadiene cis isomer: 19.9min
2, 4-hexadiene trans isomer: 21.1min
Dicyclopentadiene (2), dicyclopentadiene (ii): 61.1 min.
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| CN114636778A (en) * | 2022-03-24 | 2022-06-17 | 新兴能源科技有限公司 | Analysis method for preparing linear alpha-olefin reaction product by ethylene oligomerization |
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| CN1751008A (en) * | 2003-02-14 | 2006-03-22 | 三井化学株式会社 | Method for producing lower olefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1751008A (en) * | 2003-02-14 | 2006-03-22 | 三井化学株式会社 | Method for producing lower olefin |
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| R. PETERS ET AL: "Low-molecular-weight model study of peroxide cross-linking of ethylene–propylene–diene rubber using gas chromatography and mass spectrometry II. Addition and combination reactions", 《JOURNAL OF CHROMATOGRAPHY A》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114636778A (en) * | 2022-03-24 | 2022-06-17 | 新兴能源科技有限公司 | Analysis method for preparing linear alpha-olefin reaction product by ethylene oligomerization |
| CN114636778B (en) * | 2022-03-24 | 2024-04-19 | 新兴能源科技有限公司 | Analysis method for preparing linear alpha-olefin reaction product by ethylene oligomerization |
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