WO2024099074A1 - 利用多维气相色谱系统分析馏分中萘类化合物的方法 - Google Patents

利用多维气相色谱系统分析馏分中萘类化合物的方法 Download PDF

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WO2024099074A1
WO2024099074A1 PCT/CN2023/126444 CN2023126444W WO2024099074A1 WO 2024099074 A1 WO2024099074 A1 WO 2024099074A1 CN 2023126444 W CN2023126444 W CN 2023126444W WO 2024099074 A1 WO2024099074 A1 WO 2024099074A1
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naphthalene compounds
chromatographic column
gas chromatography
chromatography system
analyzing
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French (fr)
Inventor
史得军
陈菲
霍明辰
王春燕
何京
崔晨曦
杨晓彦
赫丽娜
喻昊
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G01N30/20—Injection using a sampling valve
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/38—Flow patterns
    • G01N30/46—Flow patterns using more than one column
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/38—Flow patterns
    • G01N30/46—Flow patterns using more than one column
    • G01N30/461—Flow patterns using more than one column with serial coupling of separation columns
    • G01N30/463—Flow patterns using more than one column with serial coupling of separation columns for multidimensional chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/60—Construction of the column
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/60—Construction of the column
    • G01N30/6034—Construction of the column joining multiple columns
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G01N30/66—Thermal conductivity detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G01N30/68—Flame ionisation detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N2030/042—Standards
    • G01N2030/045—Standards internal
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N2030/042—Standards
    • G01N2030/047—Standards external

Definitions

  • the invention relates to the technical field of petroleum fraction detection, and in particular to a method for analyzing naphthalene compounds in fractions by using a multidimensional gas chromatography system.
  • the 160-400°C fraction especially catalytic diesel, has a high aromatic content and has the potential to be used as a chemical raw material.
  • aromatics as one of the main components of crude oil, contain rich geochemical information.
  • the distribution of aromatics such as naphthalene compounds in crude oil and their carbon stable isotope composition are often used to evaluate the organic matter source and thermal maturity of crude oil.
  • conventional chromatographic analysis is limited by the separation ability and column capacity of the chromatographic column. Naphthalene compounds are prone to form "co-distillation peaks", which affect the peak area integration results. Low-content compounds are easily interfered by baseline noise and other substances and cannot be detected [Wang Huitong, Weng Na, Zhang Shuichang, Zhu Guangyou, Wei Caiyun. Comparison of geochemical parameters between comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and conventional chromatographic analysis [J]. Chinese Science: Earth Sciences, 2011, 41(11): 1586-1595.].
  • the defects of this technology or the shortcomings of the present invention are as follows: 1
  • the sample needs to be pretreated, which is time-consuming and has a low recovery rate; 2
  • the one-dimensional chromatography cannot separate 2,6-DMN from 2,7-DMN, 1,3-DMN from 1,7-DMN, It is even impossible to separate naphthalene compounds such as 1,5-DMN, 1,4-DMN, and 2,3-DMN.
  • CN112630312A discloses a method for detecting polycyclic aromatic hydrocarbons in diesel using a comprehensive two-dimensional gas chromatography-hydrogen flame ionization detector, wherein the sample does not need to be pretreated and is directly analyzed using comprehensive two-dimensional chromatography.
  • the defects of this technology or the shortcomings of the present invention are: it is mainly used to determine the composition of polycyclic aromatic hydrocarbons, and cannot effectively separate naphthalene compounds such as 2,6-DMN and 2,7-DMN, 1,3-DMN and 1,7-DMN.
  • CN1344930A discloses a method for determining the composition of carbon + heavy aromatic hydrocarbons, and discloses that: using a capillary chromatographic column filled with polydimethylsiloxane, the determination method can achieve full separation of the main components in the C9-C12 aromatic fraction.
  • the defects of this technology or the shortcomings of the present invention are: using a single non-polar chromatographic column, it is impossible to achieve baseline separation of 10 types of dimethylnaphthalene, and there is no example to support the technical solution of this patent.
  • the purpose of the present invention is to provide a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which can simultaneously obtain the monomer contents of multiple naphthalene compounds in the fraction through a single direct injection analysis, achieve baseline separation of each compound, and have high qualitative and quantitative accuracy.
  • the present invention provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, the method comprising the following steps:
  • the first chromatographic column has a length of 20-60 m, an inner diameter of 0.25-0.32 mm, and a flow rate of 0.8-2 mL/min. Select 1.1mL/min.
  • the second chromatographic column has a length of 20-60 m, an inner diameter of 0.20-0.53 mm, and a flow rate of 2-4 mL/min.
  • the second chromatographic column is selected from a chromatographic column capable of separating xylene.
  • S1 further comprises: under the control of the center-cutting component, the other hydrocarbon compounds enter the third chromatographic column and then enter the second detector for analysis.
  • the injection port is connected to the inlet of the first chromatographic column, and the outlet of the first chromatographic column is connected to the inlet of the center-cutting assembly;
  • the first outlet of the center-cutting assembly is connected to the inlet of the second chromatographic column, and the outlet of the second chromatographic column is connected to the first detector;
  • the second outlet of the center-cutting assembly is connected to the inlet of the third chromatographic column, and the outlet of the third chromatographic column is connected to the second detector.
  • the heart-cutting component further comprises: a microfluidic component, a carrier gas inlet, a damping column and a solenoid valve;
  • the microfluidic component comprises a first port, a second port and a third port;
  • the first port is formed as an inlet of the heart-cutting component, the second port is connected to the first outlet, and the third port is connected to the second outlet;
  • the heart cutting assembly has a switchable first working state and a second working state; in the first working state, the solenoid valve is in a closed state, and the carrier gas inlet is connected to the second outlet through the first carrier gas pipeline, so that the carrier gas passes through the first carrier gas pipeline, the second outlet and the components flowing out of the first chromatographic column into the third chromatographic column;
  • the solenoid valve In the second working state, the solenoid valve is in an open state, and the carrier gas inlet is connected to the first outlet through a second carrier gas pipeline, so that the carrier gas enters the second chromatographic column together with the components flowing out of the first chromatographic column through the second carrier gas pipeline and the first outlet.
  • the switching time of the solenoid valve of the center cutting is 12-12.5 minutes to open, 14-14.5 minutes to close; 15.5-16.5 minutes to open, 18.5-20 minutes to close.
  • the present invention reasonably controls the cutting time of the multidimensional gas chromatography system, effectively separates naphthalene compounds, and can improve the accuracy and stability of the analysis method.
  • the switching time of the solenoid valve of the center cutting is 12.2 min to open and 13.5 min to close; 16.5 min to open and 17.2 min to close; 17.3 min to open and 18.7 min to close; 18.9 min to open and 19.3 min to close; 19.5 min to open and 19.9 min to close. closure.
  • the temperature of the injection port is 280-310° C.
  • the injection volume is 0.1-1 ⁇ L
  • the split ratio is 80:1-250:1.
  • the third chromatographic column is a passivated empty tube column without a stationary phase
  • the resistance of the third chromatographic column is the same as that of the second chromatographic column
  • the column length is 0.5-3.0m
  • the inner diameter is 0.10-0.32mm
  • the column flow rate is 2-4mL/min.
  • the first detector is a hydrogen flame ionization detector.
  • the second detector is a thermal conductivity detector, a hydrogen flame ionization detector or direct venting.
  • the carrier gas used in the multidimensional gas chromatography system is helium or nitrogen; a programmed temperature increase operation is adopted, and the programmed temperature increase conditions include: the initial temperature is 80-120°C, the first-order heating rate is 1-3°C/min, the temperature is increased to 130-150°C, the second-order heating rate is 0.5-2°C/min, the temperature is increased to 170-190°C, and the temperature is kept constant for 5-20 minutes.
  • the external standard solution is selected from a standard solution of naphthalene, 1-methylnaphthalene or 2-methylnaphthalene, and its concentration range is 0.1wt%-10wt%.
  • the method of the present invention uses a single-point external standard of naphthalene compounds to obtain accurate and stable test results, greatly simplifying the analysis method steps.
  • the naphthalene compounds include one or more of naphthalene, methylnaphthalene, and dimethylnaphthalene (DMN).
  • the naphthalene compounds include one or more of naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-ethylnaphthalene, 1-ethylnaphthalene, 26-dimethylnaphthalene, 27-dimethylnaphthalene, 17-dimethylnaphthalene, 13-dimethylnaphthalene, 16-dimethylnaphthalene, 14-dimethylnaphthalene, 15-dimethylnaphthalene, 23-dimethylnaphthalene, 12-dimethylnaphthalene, and 18-dimethylnaphthalene.
  • the 160-400°C fraction is a 160-400°C fraction obtained by processing petroleum through petrochemical and coal chemical processes.
  • the fraction comprises at least one fraction of 160-400° C. fractions, and more preferably comprises at least one fraction of 200-250° C. fractions.
  • the fraction is selected from coal tar, ethylene tar, catalytic cracking products or aromatics.
  • the analytical method of the present invention can be used in the fields of raw material evaluation for secondary processing of fractions, oil source identification for oil exploration and development, etc.
  • the invention provides a chromatographic analysis method for the content of naphthalene compounds in a fraction using multidimensional gas chromatography analysis.
  • the method of the invention can simultaneously obtain the contents of multiple naphthalene compound monomers in the fraction by direct sampling at one time, and can especially separate dimethylnaphthalene compounds.
  • the method is simple, reliable and highly repeatable, and overcomes the problems of traditional one-dimensional chromatography and full two-dimensional chromatography analysis methods, such as the need for sample pretreatment, complex steps, long analysis time, and inability to baseline separate dimethylnaphthalene compounds.
  • FIG1 is a schematic diagram of the structure of a multidimensional gas chromatography system used in the present invention.
  • FIG. 2 is a chromatogram of naphthalene compounds in the diesel of Example 1.
  • the multidimensional gas chromatography system used in each embodiment of the present invention comprises: an injection port 1, a first chromatographic column 2, a heart-cutting assembly 3, a second chromatographic column 4, a first detector 5, a third chromatographic column 6, and a second detector 7;
  • the injection port 1 is connected to the inlet of the first chromatographic column 2, and the outlet of the first chromatographic column 2 is connected to the inlet of the center cutting component 3; the first outlet of the center cutting component 3 is connected to the inlet of the second chromatographic column 4, and the outlet of the second chromatographic column 4 is connected to the first detector 5; the second outlet of the center cutting component 3 is connected to the inlet of the third chromatographic column 6, and the outlet of the third chromatographic column 6 is connected to the second detector 7.
  • the center cutting component 3 also includes: a microfluidic component, a carrier gas inlet, a damping column and a solenoid valve;
  • the microfluidic component includes a first port, a second port and a third port;
  • the first port is formed as the inlet of the center cutting component 3, the second port is connected to the first outlet, and the third port is connected to the second outlet;
  • the center cutting component 3 has a switchable first working state and a second working state; in the first working state, the solenoid valve is in a closed state, and the carrier gas inlet is connected to the second outlet through a first carrier gas pipeline, so as to allow the carrier gas to pass through the first carrier gas pipeline, the second outlet and the components flowing out of the first chromatographic column 2 to enter the third chromatographic column 6; in the second working state, the solenoid valve is in an open state, and the carrier gas inlet is connected to the first outlet through a second carrier gas pipeline, so as to allow the carrier gas to pass through the second carrier gas pipeline, the
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 280°C
  • the injection volume is 0.1 ⁇ L
  • the split ratio is 150:1.
  • the first chromatographic column 2 is a chromatographic column with a 0% phenyl dimethyl polysiloxane stationary phase, with a specification of 15m ⁇ 0.25mm ⁇ 0.25 ⁇ m and a flow rate of 1.1mL/min.
  • the valve switching time of the central cutting component 3 is 12.2min open, 13.5min closed; 16.5min open, 17.2min closed; 17.3min open, 18.7min closed; 18.9min open, 19.3min closed; 19.5min open, 19.9min closed.
  • the second chromatographic column 4 is a stationary phase preferably with 10% ⁇ -cyclodextrin bonded (20%-cyanopropyl-phenyl)-methyl polysiloxane, with a specification of 60m ⁇ 0.25mm ⁇ 0.25 ⁇ m, a column flow rate of 2.5mL/min for 20min, and then reduced from 20mL/ min2 to 2.0mL/min to maintain until the end of the analysis.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with a specification of 1.5m ⁇ 0.1mm, a column flow rate of 2.5mL/min for 20min, and then reduced from 20mL/ min2 to 2.0mL/min to maintain until the end of the analysis.
  • the first detector 5 is a hydrogen flame ionization detector
  • the second detector 7 is a thermal conductivity detector.
  • the chromatographic system uses helium as a carrier gas, and the program temperature is operated.
  • the initial temperature of the program temperature condition is 80°C
  • the first-order temperature rise rate is 2°C/min
  • the temperature is raised to 140°C
  • the second-order temperature rise rate is 1°C/min
  • the temperature is raised to 170°C, and the temperature is kept constant for 5min.
  • the chromatogram of naphthalene compounds is shown in Figure 2.
  • a diesel solution with a 1-methylnaphthalene concentration of 5.02% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 1.
  • the entire chromatographic quantitative analysis process took 1 hour.
  • the external standard sample and the diesel sample to be tested were analyzed once under the same chromatographic conditions to examine the repeatability of the method. The results are shown in Table 1.
  • the accuracy of this method was investigated by the spiked recovery rate of 2-methylnaphthalene.
  • Two more samples of catalytic cracking diesel from a petrochemical company were taken, one of which was spiked with 1.56% 2-methylnaphthalene.
  • the content of 2-methylnaphthalene in both samples was determined according to the aforementioned multidimensional analysis method.
  • the ratio of the difference between the content of 2-methylnaphthalene in the spiked sample and the content of 2-methylnaphthalene in the unspiked sample and the theoretical value of the added 2-methylnaphthalene is the spiked recovery rate, which is 98.9%. This shows that the spiked recovery rate of the sample determined by this method is high and the accuracy of the method is good.
  • This method can simultaneously catalyze the content of naphthalene compounds in diesel, and it can be seen from the chromatogram that the naphthalene compounds are basically baseline separated.
  • the method is simple, accurate and reliable and is suitable for the analysis of naphthalene compounds in catalytic cracking diesel.
  • This comparative example provides an analysis method for naphthalene compounds in a fraction, which is as follows:
  • the aromatic components in the catalytic cracking diesel of Example 1 were separated as the sample to be analyzed.
  • the content of naphthalene compounds in diesel aromatics was analyzed by gas chromatography-hydrogen flame ionization detector.
  • a chromatographic column with a 0% phenyl dimethyl polysiloxane stationary phase was used, with specifications of 30m ⁇ 0.25mm ⁇ 0.25 ⁇ m, an injection volume of 1.0 ⁇ L, an injection port temperature of 300°C, a split ratio of 15:1, a carrier gas of helium, a flow rate of 1.5mL/min, an initial temperature of the chromatographic column box of 60°C, maintained for 2min, and raised to 300°C at 5°C/min, and kept constant for 5min.
  • a diesel solution with a 1-methylnaphthalene concentration of 5.02% was prepared as an external standard solution by the standard addition method. The external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 2.
  • the accuracy of this method was investigated by the spiked recovery of 2-methylnaphthalene.
  • Two samples of catalytic cracking diesel from a petrochemical company were taken, one of which was added with 1.56% 2-methylnaphthalene as a spiked sample.
  • the content of 2-methylnaphthalene was determined for both samples according to the method of Comparative Example 1.
  • the ratio of the difference between the content of 2-methylnaphthalene in the spiked sample and the theoretical value of the added 2-methylnaphthalene was 85.9%. It can be seen that the spiked recovery of the sample measured by the method described in Comparative Example 1 is relatively low, indicating that due to the pretreatment process, the content information of naphthalene compounds is lost and the measurement results are low.
  • This comparative example provides an analysis method for naphthalene compounds in a fraction, which is as follows:
  • the aromatic components in the catalytic cracking diesel in Example 1 were separated according to the SH/T 0606-2005 method as the sample to be analyzed.
  • the comprehensive two-dimensional gas chromatography (GC ⁇ GC) was produced by LECO, USA.
  • the GC ⁇ GC system consisted of an Agilent 7890 gas chromatograph equipped with a hydrogen flame ionization detector (FID) and a dual-nozzle thermal modulator, and the data processing system was Chroma TOF software.
  • the chromatographic columns were all products of Agilent Technologies, Inc., USA.
  • the analysis conditions of the comprehensive two-dimensional chromatography system were as follows: the one-dimensional chromatographic column was a chromatographic column with 0% phenyl dimethylpolysiloxane stationary phase, 50m ⁇ 0.2mm ⁇ 0.5 ⁇ m, and the two-dimensional column was a chromatographic column with (50%-phenyl)-methylpolysiloxane stationary phase, 3m ⁇ 0.1mm ⁇ 0.1 ⁇ m; the temperature program of the one-dimensional column was 80°C for 0.2min, then increased to 310°C at 2°C/min and maintained for 25min; the temperature program of the two-dimensional column was 90°C for 0.2min, then increased to 320°C at 2°C/min and maintained for 25min; the injection port temperature was 300°C, the injection volume was 1 ⁇ L, the split ratio was 50:1, the carrier gas was helium, the flow rate was 1.8mL/min, the modulator temperature was 30°C higher than the one-dimensional furnace temperature, the modulation period was 10s, of which 2.5s was the hot blow
  • a diesel solution with a 1-methylnaphthalene concentration of 5.02% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 3.
  • the diesel sample to be tested was analyzed once using the same method to examine the repeatability of the method, and the results are shown in Table 3.
  • the accuracy of this method was investigated by the spiked recovery of 2-methylnaphthalene.
  • Two samples of catalytic cracking diesel from a petrochemical company were taken, one of which was spiked with 1.56% 2-methylnaphthalene.
  • the content of 2-methylnaphthalene was determined for both samples according to the method of Comparative Example 2.
  • the ratio of the difference between the content of 2-methylnaphthalene in the spiked sample and the theoretical value of the added 2-methylnaphthalene was 86.3%. It can be seen that the spiked recovery of the sample measured by the method described in Comparative Example 2 is relatively low, indicating that due to the pretreatment process, the content information of naphthalene compounds is lost and the measurement result is low.
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 290°C
  • the injection volume is 0.5 ⁇ L
  • the split ratio is 250:1.
  • the first chromatographic column 2 is a chromatographic column with a 5% phenyl dimethyl polysiloxane stationary phase, with a specification of 60m ⁇ 0.25mm ⁇ 0.5 ⁇ m and a flow rate of 2mL/min.
  • the valve switching time of the center cutting component 3 is 12min open, 14min closed; 16min open, 20min closed.
  • the second chromatographic column 4 is a stationary phase preferably with 5% ⁇ -cyclodextrin bonded- Methylpolysiloxane, specifications are 50m ⁇ 0.25mm ⁇ 0.25 ⁇ m, and the column flow rate is 4mL/min.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with specifications of 1.28m ⁇ 0.1mm and a column flow rate of 4mL/min.
  • the first detector 5 is a hydrogen flame ionization detector
  • the second detector 7 is a hydrogen flame ionization detector.
  • the chromatographic system uses helium as a carrier gas and is programmed to operate at a high temperature.
  • the initial temperature of the programmed temperature increase condition is 90°C, and the temperature is increased to 140°C at a first-order temperature increase rate of 1°C/min, and then increased to 180°C at 1°C/min, and kept at a constant temperature for 20min.
  • a diesel solution with a naphthalene concentration of 0.10% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 4. The entire chromatographic quantitative analysis process took 2 hours.
  • This comparative example provides an analysis method for naphthalene compounds in a fraction, which is as follows:
  • the aromatic components in the catalytic cracking diesel in Example 1 were separated as the sample to be analyzed.
  • the injection port temperature was 290°C
  • the injection volume was 0.5 ⁇ L
  • the split ratio was 250:1.
  • the chromatographic column preferably added 8% ⁇ -cyclodextrin-bonded methylpolysiloxane as the stationary phase, with a specification of 50m ⁇ 0.25mm ⁇ 0.25 ⁇ m and a column flow rate of 4mL/min.
  • the detector was a hydrogen flame ionization detector.
  • the chromatographic system used helium as the carrier gas and was programmed to heat up.
  • the initial temperature of the programmed temperature increase condition was 90°C, and the temperature was increased to 140°C at a first-order heating rate of 1°C/min, and then at 1°C.
  • the temperature was raised to 220°C at 1000 rpm and kept constant for 50 min. The whole analysis process took 3.5 h.
  • a diesel solution with a naphthalene concentration of 0.10% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions. The analysis results are shown in Table 5.
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 300°C
  • the injection volume is 1 ⁇ L
  • the split ratio is 80:1.
  • the first chromatographic column 2 is a 3% phenyl dimethylpolysiloxane chromatographic column with a specification of 30m ⁇ 0.32mm ⁇ 0.25 ⁇ m and a flow rate of 0.8mL/min.
  • the valve switching time of the central cutting component 3 is 12.5min to open, 14.5min to close; 15.5min to open, and 18.5min to close.
  • the second chromatographic column 4 is a stationary phase preferably with 15% ⁇ -cyclodextrin bonded -methylpolysiloxane added, with a specification of 60m ⁇ 0.32mm ⁇ 0.5 ⁇ m, and a column flow rate of 2mL/min.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with a specification of 3.0m ⁇ 0.15mm, and a column flow rate of 2mL/min.
  • the first detector 5 is a hydrogen flame ionization detector, and the second detector 7 is vented (not connected to the detector).
  • the chromatographic system uses nitrogen as the carrier. The temperature was raised to 150 °C at a rate of 3 °C/min, then to 190 °C at a rate of 2 °C/min, and kept at this temperature for 10 min.
  • a diesel solution with a 10.0% 1-methylnaphthalene concentration was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 6.
  • the entire chromatographic quantitative analysis process took 1 hour.
  • the external standard sample and the diesel sample to be tested were analyzed once under the same chromatographic conditions to examine the repeatability of the method, and the results are shown in Table 6.
  • the accuracy of this method was investigated by the spiked recovery rate of 1-methylnaphthalene.
  • Two samples of hydrogenated diesel from a petrochemical company were taken, one of which was spiked with 53.65 mg/kg of 2-methylnaphthalene.
  • the content of 1-methylnaphthalene was determined for both samples according to the aforementioned multidimensional analysis method.
  • the ratio of the difference between the content of 1-methylnaphthalene in the spiked sample and the content of 1-methylnaphthalene in the unspiked sample to the theoretical value of the added 1-methylnaphthalene is the spiked recovery rate, which is 101.2%. It can be seen that the spiked recovery rate of the sample determined by this method is relatively high, indicating that the accuracy of the method is good.
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 310°C
  • the injection volume is 0.2 ⁇ L
  • the split ratio is 200:1.
  • the first chromatographic column 2 is a chromatographic column of 4% phenyl dimethyl polysiloxane, with a specification of 25m ⁇ 0.32mm ⁇ 0.25 ⁇ m and a flow rate of 1.5mL/min.
  • the valve switching time of the center cutting component 3 is 12.3min to open, 14.3min to close; 16.5min to open, and 19min to close.
  • the second chromatographic column 4 is a stationary phase preferably with 20% ⁇ -cyclodextrin bonded methyl polysiloxane added, with a specification of 50m ⁇ 0.53mm ⁇ 1 ⁇ m, and a column flow rate of 3mL/min.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with a specification of 2.5m ⁇ 0.25mm, and a column flow rate of 3mL/min.
  • the first detector 5 is a hydrogen flame ionization detector
  • the second detector 7 is a hydrogen flame ionization detector.
  • the chromatographic system used nitrogen as carrier gas and programmed temperature operation. The initial temperature of the programmed temperature was 90°C, and the temperature was increased to 140°C at a first-order heating rate of 2°C/min, then increased to 180°C at 0.5°C/min, and maintained at a constant temperature for 10 minutes.
  • a diesel solution with a 2-methylnaphthalene concentration of 6.32% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 7. The entire chromatographic quantitative analysis process took 1 hour.
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 300°C
  • the injection volume is 0.5 ⁇ L
  • the split ratio is 100:1.
  • the first chromatographic column 2 is a chromatographic column of 2% phenyl dimethyl polysiloxane, with a specification of 40m ⁇ 0.25mm ⁇ 1 ⁇ m and a flow rate of 1.5mL/min.
  • the valve switching time of the center cutting component 3 is 12.1min to open, 14.4min to close; 16.1min to open, and 19.3min to close.
  • the second chromatographic column 4 is a stationary phase preferably adding 11% ⁇ -cyclodextrin bonded-50% phenyl-methyl polysiloxane, with a specification of 20m ⁇ 0.25mm ⁇ 1 ⁇ m, and a column flow rate of 4mL/min, which is maintained for 20min and then reduced to 2.0mL/min from 20mL/min 2 until the end of the analysis.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with a specification of 0.50m ⁇ 0.1mm, and a column flow rate of 4mL/min, which is maintained for 20min and then reduced to 2.0mL/min from 20mL/ min2 until the end of the analysis.
  • the first detector 5 is a hydrogen flame ionization detector
  • the second detector 7 is a hydrogen flame ionization detector.
  • the chromatographic system uses helium as a carrier gas and is operated by programmed temperature rise.
  • the initial temperature of the programmed temperature rise condition is 80°C, and the temperature is raised to 130°C at a first-order heating rate of 1.5°C/min, and then raised to 170°C at 0.5°C/min, and kept at a constant temperature for 5min.
  • a diesel solution with a 1-methylnaphthalene concentration of 0.18% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 8. The entire chromatographic quantitative analysis process took 1 hour.
  • This embodiment provides a method for analyzing naphthalene compounds in a fraction using a multidimensional gas chromatography system, which is as follows:
  • the injection port temperature is 300 ° C
  • the injection volume is 0.5 ⁇ L
  • the split ratio is 100: 1.
  • the first chromatographic column 2 is a chromatographic column with a 0% phenyl dimethyl polysiloxane stationary phase, with a specification of 20m ⁇ 0.53mm ⁇ 0.25 ⁇ m and a flow rate of 1.5mL/min.
  • the valve switching time of the center cutting component 3 is 12min open, 14min closed; 16min open, 20min closed.
  • the second chromatographic column 4 is a stationary phase preferably adding 11% ⁇ -cyclodextrin bonded (10%-cyanopropyl-30% phenyl)-methyl polysiloxane, with a specification of 40m ⁇ 0.25mm ⁇ 0.25 ⁇ m, and a column flow rate of 4mL/min.
  • the third chromatographic column 6 is a passivated empty tube column without a stationary phase, with a specification of 1.0m ⁇ 0.1mm, and a column flow rate of 4mL/min.
  • the first detector 5 is a hydrogen flame ionization detector
  • the second detector 7 is a hydrogen flame ionization detector.
  • the chromatographic system used helium as carrier gas and programmed temperature operation. The initial temperature of the programmed temperature was 80°C, and the temperature was increased to 130°C at a first-order heating rate of 1.5°C/min, then increased to 170°C at 0.5°C/min, and kept constant for 5 minutes.
  • a diesel solution with a 1-methylnaphthalene concentration of 6.89% was prepared as an external standard solution by the standard addition method.
  • the external standard sample and the diesel sample to be tested were analyzed under the same chromatographic conditions, and the analysis results are shown in Table 9. The entire chromatographic quantitative analysis process took 1 hour.
  • This comparative example provides an analysis method for naphthalene compounds in a fraction, which is as follows:
  • Example 6 The sample in Example 6 was analyzed by the method described in the specific implementation of CN1344930A.
  • the chromatographic conditions were as follows: the chromatographic column stationary phase was polydimethylsiloxane, with a specification of 60m ⁇ 0.25mm ⁇ 0.5 ⁇ m, helium as carrier gas, programmed temperature rise operation, initial temperature 100°C, then raised to 130°C at a heating rate of 5°C/min, stayed for 10min, then raised to 200°C at a heating rate of 15°C/min, stayed for 15min, and finally raised to 280°C at a heating rate of 20°C/min, stayed for 30min; the vaporization chamber temperature was 250°C, the injection port temperature was 300°C, the split ratio was 100:1, and the column head pressure was 138kPa.
  • Table 10 The analysis results are shown in Table 10.
  • the CN1344930A method cannot achieve baseline separation of naphthalene compounds, and some hydrocarbon compounds co-elute with naphthalene compounds, resulting in a high analysis result.

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Abstract

一种利用多维气相色谱系统分析馏分中萘类化合物的方法，包括：使待测样品经所述多维气相色谱系统分的进样口进入第一色谱柱，分离出萘类化合物和其他烃类化合物；在中心切割组件控制下，所述萘类化合物进入第二色谱柱，然后进入第一检测器进行分析，得到样品检测图谱；对样品中萘类化合物进行定性分析与定量分析。本发明的方法一次直接进样可以同时得到馏分中15种萘类化合物单体含量，尤其能够分离二甲基萘类化合物，方法简单、可靠，重复性高。

Description

利用多维气相色谱系统分析馏分中萘类化合物的方法 技术领域
本发明涉及石油馏分检测技术领域，具体涉及一种利用多维气相色谱系统分析馏分中萘类化合物的方法。
背景技术
随着市场对油品的需求结构发生了巨大变化：汽油、航煤需求增加，柴油需求量回落，石脑油呈供不应求的局面。目前柴油过剩将成为常态，如何将过剩柴油加工成化工原料或是高附加值的动力燃料成为炼厂提高经济效益的重要挑战。160-400℃的馏分、尤其是催化柴油芳烃含量较高，具有作为化工原料的潜力。
目前已有报道将催化柴油中富含的多环芳烃转化成轻芳烃，从而降低柴汽比及增产苯、甲苯、二甲苯等基础化工原料工艺路线[崔宝静.催化柴油转化生产轻芳烃技术研究进展[J].当代化工,2021,50(08):1962-1966.]。此外，随着高级芳香聚合材料的迅速发展，新型聚合材料的研究重点己由脂肪族高聚物转向了链上带有苯环的高聚物，并且由带苯环的转向了带有萘环的高聚物的研究。因此，也有从柴油中直接提取高附加值化合物的报道。以最具有代表性的化合物2,6-二甲基萘(2,6-DMN)为例，它是合成含萘聚合物的重要原料，其氧化后生成的2,6-萘二甲酸与乙二醇聚合制得的聚萘二甲酸乙二醇酯是一种新型的聚酯型材料，在耐热性、机械性能、阻气性、化学稳定性以及耐辐射性上具有较为优越的表现，广泛应用于电子元件、仪器仪表、绝缘材料等行业，应用前景非常广阔[孙学文,刘彦辉.从催化裂化柴油中分离高纯度2,6-二甲基萘[J].精细石油化工,2002(05):26-28.]。
此外，芳烃作为原油的主要组分之一，蕴含丰富的地球化学信息，常用原油中萘类化合物等芳烃分布及其碳稳定同位素组成来评价原油的有机质来源和热成熟度等指标。不过常规色质在分析时受色谱柱分离能力和柱容量的限制，萘类化合物等易形成“共馏峰”，影响峰面积积分结果，低含量的化合物易受基线噪音和其他物质的干扰而无法检出[王汇彤,翁娜,张水昌,朱光有,魏彩云.全二维气相色谱/飞行时间质谱与常规色质分析的地球化学参数对比[J].中国科学:地球科学,2011,41(11):1586-1595.]。
现有技术中，[原油中多环芳烃内标法指纹分析[J].分析测试学报,2008(04):344-348]公开了：柴油样品经过预处理，分离为饱和烃和芳烃两部分，芳烃部分进一维色谱分析萘类化合物含量。该技术的缺陷或相对本发明的不足之处：①样品需要预处理，耗时长，回收率低；②采用一维色谱，无法分离2,6-DMN与2,7-DMN，1,3-DMN与1,7-DMN， 甚至无法分离1,5-DMN、1,4-DMN、2,3-DMN等萘类化合物。
[全二维气相色谱/飞行时间质谱与常规色质分析的地球化学参数对比[J].中国科学:地球科学,2011,41(11):1586-1595]，公开了：柴油样品经过预处理，分离为饱和烃和芳烃两部分，芳烃部分采用全二维色谱进行分析。该技术的缺陷或相对本发明的不足之处：①样品需要预处理，耗时长，回收率低；②采用一维色谱，无法分离2,6-DMN与2,7-DMN，1,3-DMN与1,7-DMN等萘类化合物。
CN112630312A公开了一种用全二维气相色谱-氢火焰离子化检测器对柴油中多环芳烃的检测方法，其中，样品不需要预处理，直接采用全二维色谱进行分析。该技术的缺陷或相对本发明的不足之处：主要用于测定多环芳烃族组成，无法有效分离2,6-DMN与2,7-DMN，1,3-DMN与1,7-DMN等萘类化合物。
CN1344930A公开了一种碳+重芳烃烃类组成的测定方法，公开了：采用填充物为聚二甲基硅氧烷的毛细管色谱柱，测定方法能够达到C9-C12芳烃馏分中主要组分的全分离。该技术的缺陷或是相对本发明的不足之处：采用单根非极性色谱柱，无法实现10种二甲基萘的基线分离，并且无实施例支持该专利的技术方案。
发明内容
为解决上述技术问题，本发明目的在于提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，一次直接进样分析可以同时得到馏分中多种萘类化合物单体含量，实现各化合物的基线分离，定性、定量准确度高。
为达到上述目的，本发明提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，所述方法包括如下步骤：
S1：使待测样品经所述多维气相色谱系统分的进样口进入第一色谱柱，分离出萘类化合物和其他烃类化合物；在中心切割组件控制下，所述萘类化合物进入第二色谱柱，然后进入第一检测器进行分析，得到样品检测图谱；其中，所述第一色谱柱的固定相为苯基含量为0-5％的二甲基聚硅氧烷，所述第二色谱柱的固定相为添加5％-20％β-环糊精键合的-甲基聚硅氧烷；
S2：将所述样品检测图谱与在相同色谱条件下得到萘类化合物标准品保留时间对比，进行定性分析；
S3：在相同色谱条件下分析萘类化合物的外标溶液，根据外标法对样品中萘类化合物进行定量分析。
上述利用多维气相色谱系统分析160-400℃馏分中萘类化合物的方法中，优选地，所述第一色谱柱的柱长为20-60m，内径为0.25-0.32mm，流量为0.8-2mL/min，更优 选为1.1mL/min。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述第二色谱柱的柱长为20-60m，内径为0.20-0.53mm，流量为2-4mL/min。在本发明中，第二色谱柱选自能够分离二甲萘的色谱柱。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，S1还包括：在中心切割组件控制下，所述其他烃类化合物进入第三色谱柱，然后进入第二检测器进行分析。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述多维气相色谱系统中，进样口与第一色谱柱的入口连通，第一色谱柱的出口与中心切割组件的入口连通；所述中心切割组件的第一出口与第二色谱柱的入口连通，第二色谱柱的出口与第一检测器连通；所述中心切割组件的第二出口与第三色谱柱的入口连通，第三色谱柱的出口与第二检测器连通。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述中心切割组件还包括：微流控组件、载气入口、阻尼柱和电磁阀；
其中，所述微流控组件包括第一端口、第二端口和第三端口；所述第一端口形成为所述中心切割组件的入口，所述第二端口与所述第一出口连通，所述第三端口与所述第二出口连通；
所述中心切割组件具有可切换的第一工作状态和第二工作状态；在所述第一工作状态，所述电磁阀处于关闭状态，所述载气入口通过第一载气管路与所述第二出口连通，用于使载气通过第一载气管路、所述第二出口与流出第一色谱柱的组分一起进入第三色谱柱；
在所述第二工作状态，所述电磁阀处于开启状态，所述载气入口通过第二载气管路与所述第一出口连通，用于使所述载气通过第二载气管路、所述第一出口与流出第一色谱柱的组分一起进入所述第二色谱柱。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述中心切割的电磁阀的切换时间为12-12.5min打开，14-14.5min关闭；15.5-16.5min打开，18.5-20min关闭。本发明合理控制多维气相色谱系统的切割时间，有效分离出萘类化合物，可提高分析方法的准确度和稳定性。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述中心切割的电磁阀的切换时间为12.2min打开，13.5min关闭；16.5min打开，17.2min关闭；17.3min打开，18.7min关闭；18.9min打开，19.3min关闭；19.5min打开，19.9min 关闭。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述进样口的温度为280-310℃，进样量为0.1-1μL，分流比为80:1-250:1。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述第三色谱柱为钝化无固定相的空管柱，第三色谱柱阻力与所述第二色谱柱相同，柱长为0.5-3.0m，内径为0.10-0.32mm，柱流量为2-4mL/min。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述第一检测器为氢火焰离子化检测器。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述第二检测器为热导检测器、氢火焰离子化检测器或是直接放空。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，多维气相色谱系统所用载气为氦气或氮气；采用程序升温操作，程序升温条件包括：初温为80-120℃，一阶升温速度为1-3℃/min，升温至130-150℃，二阶升温速度为0.5-2℃/min，升温至170-190℃，恒温5-20min。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述外标溶液选自萘、1-甲基萘或2-甲基萘的标准品溶液，其浓度范围为0.1wt％-10wt％。本发明的方法选用一种萘类化合物的单点外标即可获得准确、稳定的测试结果，大大简化了分析方法步骤。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述萘类化合物包括萘、甲基萘、二甲基萘(DMN)中的一种或多种。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述萘类化合物包括萘、1-甲基萘、2-甲基萘、2-乙基萘、1-乙基萘、26-二甲基萘、27-二甲基萘、17-二甲基萘、13-二甲基萘、16-二甲基萘、14-二甲基萘、15-二甲基萘、23-二甲基萘、12-二甲基萘、18-二甲基萘中的一种或多种。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述160-400℃馏分为石油经石油化工、煤化工工艺加工得到的160-400℃馏分。
上述利用多维气相色谱系统分析馏分中萘类化合物的方法中，优选地，所述馏分包含160-400℃馏分中的至少一种馏分；更优选包含200-250℃馏分中的至少一种馏分。所述馏分选自煤焦油、乙烯焦油、催化裂解产品或芳烃。
本发明的分析方法可以用于的馏分二次加工的原料评价、石油勘探开发的油源鉴定等领域。
本发明提供的技术方案，具有如下有益效果：
本发明提供了一种采用多维气相色谱分析的馏分萘类化合物含量的色谱分析方法，通过选用合适的色谱柱，并合理控制切割时间，使得本发明的方法一次直接进样可以同时得到馏分中多种萘类化合物单体含量，尤其能够分离二甲基萘类化合物，方法简单、可靠，重复性高，克服了传统一维色谱、全二维色谱分析方法需要样品预处理、步骤复杂、分析时间长、无法基线分离二甲基萘类化合物等问题。
附图说明
图1为本发明所用多维气相色谱系统的结构示意图；
图2为实施例1的柴油中萘类化合物色谱图。
图1中附图标号说明：
1、进样口；2、第一色谱柱；3、中心切割组件；4、第二色谱柱；5、第一检测器；
6、第三色谱柱；7、第二检测器。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
如图1所示，本发明各实施例中采用的多维气相色谱系统包括：进样口1、第一色谱柱2、中心切割组件3、第二色谱柱4、第一检测器5、第三色谱柱6、第二检测器7；
其中，进样口1与第一色谱柱2的入口连通，第一色谱柱2的出口与中心切割组件3的入口连通；所述中心切割组件3的第一出口与第二色谱柱4的入口连通，第二色谱柱4的出口与第一检测器5连通；所述中心切割组件3的第二出口与第三色谱柱6的入口连通，第三色谱柱6的出口与第二检测器7连通。
其中，所述中心切割组件3还包括：微流控组件、载气入口、阻尼柱和电磁阀；所述微流控组件包括第一端口、第二端口和第三端口；所述第一端口形成为所述中心切割组件3的入口，所述第二端口与所述第一出口连通，所述第三端口与所述第二出口连通；所述中心切割组件3具有可切换的第一工作状态和第二工作状态；在所述第一工作状态，所述电磁阀处于关闭状态，所述载气入口通过第一载气管路与所述第二出口连通，用于使载气通过第一载气管路、所述第二出口与流出第一色谱柱2的组分一起进入第三色谱柱6；在所述第二工作状态，所述电磁阀处于开启状态，所述载气入口通过第二载气管路与所述第一出口连通，用于使所述载气通过第二载气管路、所述第一出口与流出第一色谱柱2的组分一起进入所述第二色谱柱4。
下面结合具体实施例描述本发明。
实施例1
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某石化催化裂化柴油作为分析样品。进样口温度为280℃，进样量为0.1μL，分流比为150:1。第一色谱柱2为0％苯基的二甲基聚硅氧烷固定相的色谱柱，规格15m×0.25mm×0.25μm，流量为1.1mL/min。中心切割组件3的阀切换时间为12.2min打开，13.5min关闭；16.5min打开，17.2min关闭；17.3min打开，18.7min关闭；18.9min打开，19.3min关闭；19.5min打开，19.9min关闭。第二色谱柱4为固定相优选添加10％β-环糊精键合的(20％-氰丙基-苯基)-甲基聚硅氧烷，规格为60m×0.25mm×0.25μm，柱流量为2.5mL/min保持20min，后以20mL/min2降至2.0mL/min保持至分析结束。所述第三色谱柱6为钝化无固定相的空管柱，规格为1.5m×0.1mm，柱流量为2.5mL/min保持20min，后以20mL/min2降至2.0mL/min保持至分析结束。第一检测器5为氢火焰离子化检测器，第二检测器7为热导检测器。色谱系统采用氦气做载气，程序升温操作，程序升温条件的初温为80℃，以一阶升温速度为2℃/min，升温至140℃，后二阶升温速度为1℃/min，升温至170℃，恒温5min。在此条件下，萘类化合物色谱图如图2所示。
通过标准加入法配置1-甲基萘浓度为5.02％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表1。整个色谱定量分析过程1h。采用相同色谱条件，重复分析外标样品和待测柴油样品1次，考察方法的重复性，结果见表1。
表1 多维色谱法分析催化柴油萘类化合物含量结果

从表1可见，两次分析结果的最小相对误差为0％，最高为1.15％，说明本方法的重复性较好。
以2-甲基萘加标回收率考察本方法的准确性。再取两份某石化催化裂化柴油样品，其中一份加入1.56％的2-甲基萘作为加标样品。两份样品均按照前述多维分析方法分别测定2-甲基萘的含量。加标样品中2-甲基萘含量减去未加标样品2-甲基萘含量，其差值同加入的2-甲基萘的理论值之比即为加标回收率，其值为98.9％。由此可见，本方法测定样品的加标回收率较高，方法的准确性好。
本方法可以同时催化柴油中萘类化合物含量，并且从色谱图中可以看出萘类化合物基本实现基线分离，方法简单、准确、可靠，适合于催化裂化柴油萘类化合物分析。
对比例1
本对比例提供一种馏分中萘类化合物的分析方法，具体如下：
按照SH/T 0606-2005方法分离实施例1催化裂化柴油中的芳烃组分，作为待分析样。气相色谱-氢火焰离子化检测器分析柴油芳烃中萘类化合物含量。采用0％苯基的二甲基聚硅氧烷固定相的色谱柱，规格为30m×0.25mm×0.25μm，进样量1.0μL，进样口温度300℃，分流比15:1，载气为氦气，流速为1.5mL/min，色谱柱箱初始温度60℃，保持2min，以5℃/min升至300℃，恒温5min。通过标准加入法配置1-甲基萘浓度为5.02％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表2。
表2 一维色谱法分析催化柴油萘类化合物含量结果

由表2可见，一维色谱无法实现萘类化合物的基线分离，部分二甲基萘类化合物共流出，无法实现所有二甲基萘类化合物基线分离。采用相同方法，重复分析待测柴油样品1次，考察方法的重复性，结果见表2。从表2可见，两次分析结果的最小相对误差为4.91％，最高可达25％，说明本方法的重复性较差。
以2-甲基萘加标回收率考察本方法的准确性。再取两份某石化催化裂化柴油样品，其中一份加入1.56％的2-甲基萘作为加标样品。两份样品均按照前述对比例1方法分别测定2-甲基萘的含量。加标样品中2-甲基萘含量减去未加标样品2-甲基萘含量，其差值同加入的2-甲基萘的理论值之比即为加标回收率，其值为85.9％。由此可见，对比例1所述方法测定样品的加标回收率较低，说明由于经过预处理过程，萘类化合物含量信息存在丢失、测定结果偏低。
对比例2
本对比例提供一种馏分中萘类化合物的分析方法，具体如下：
按照SH/T 0606-2005方法分离实施例1中催化裂化柴油中的芳烃组分，作为待分析样。全二维气相色谱(GC×GC)由美国LECO公司生产，GC×GC系统由配有氢火焰离子化检测器(FID)的Agilent7890气相色谱仪和双喷口热调制器组成，数据处理系统为Chroma TOF软件。色谱柱均为美国安捷伦科技有限公司产品，全二维色谱系统分析条件为：一维色谱柱为0％苯基的二甲基聚硅氧烷固定相的色谱柱，50m×0.2mm×0.5μm，二维柱为(50％-苯基)-甲基聚硅氧烷固定相的色谱柱，3m×0.1mm×0.1μm；一维柱升温程序为80℃保持0.2min，然后以2℃/min升高至310℃保持25min；二维柱升温程序为90℃保持0.2min，然后以2℃/min升高至320℃保持25min；进样口温度300℃，进样量1μL，分流比50:1，载气为氦气，流量为1.8mL/min，调制器温度比一维炉温高30℃，调制周期为10s，其中2.5s为热吹时间。
通过标准加入法配置1-甲基萘浓度为5.02％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表3。采用相同方法，重复分析待测柴油样品1次，考察方法的重复性，结果见表3。
表3 全二维色谱法分析催化柴油萘类化合物含量结果
从表3可见，两次分析结果的最小相对误差为4.40％，最高可达18.75％，说明本方法的重复性较差；全二维色谱无法实现萘类化合物的基线分离，部分二甲基萘类化合物共流出。
以2-甲基萘加标回收率考察本方法的准确性。再取两份某石化催化裂化柴油样品，其中一份加入1.56％的2-甲基萘作为加标样品。两份样品均按照前述对比例2方法分别测定2-甲基萘的含量。加标样品中2-甲基萘含量减去未加标样品2-甲基萘含量，其差值同加入的2-甲基萘的理论值之比即为加标回收率，其值为86.3％。由此可见，对比例2所述方法测定样品的加标回收率较低，说明由于经过预处理过程，萘类化合物含量信息存在丢失、测定结果偏低。
实施例2
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某石化直馏柴油作为分析样品。进样口温度为290℃，进样量为0.5μL，分流比为250:1。第一色谱柱2为5％苯基的二甲基聚硅氧烷固定相的色谱柱，规格60m×0.25mm×0.5μm，流量为2mL/min。中心切割组件3的阀切换时间为12min打开，14min关闭；16min打开，20min关闭。第二色谱柱4为固定相优选添加5％β-环糊精键合的- 甲基聚硅氧烷，规格为50m×0.25mm×0.25μm，柱流量为4mL/min。所述第三色谱柱6为钝化无固定相的空管柱，规格为1.28m×0.1mm，柱流量为4mL/min。第一检测器5为氢火焰离子化检测器，第二检测器7为氢火焰离子化检测器。色谱系统采用氦气做载气，程序升温操作，程序升温条件的初温为90℃，以一阶升温速度为1℃/min升温至140℃，然后以1℃/min升温至180℃，恒温20min。
通过标准加入法配置萘浓度为0.10％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表4。整个色谱定量分析过程2h。
表4 多维色谱法分析直馏柴油萘类化合物含量结果
对比例3
本对比例提供一种馏分中萘类化合物的分析方法，具体如下：
按照SH/T 0606-2005方法分离实施例1中催化裂化柴油中的芳烃组分，作为待分析样。进样口温度为290℃，进样量为0.5μL，分流比为250:1。色谱柱为固定相优选添加8％β-环糊精键合的-甲基聚硅氧烷，规格为50m×0.25mm×0.25μm，柱流量为4mL/min。检测器为氢火焰离子化检测器。色谱系统采用氦气做载气，程序升温操作，程序升温条件的初温为90℃，以一阶升温速度为1℃/min升温至140℃，然后以1℃ /min升温至220℃，恒温50min。整个过程分析过程耗时3.5h。
通过标准加入法配置萘浓度为0.10％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品、待测柴油样品，分析结果见表5。
表5 全二维色谱法分析催化柴油萘类化合物含量结果
由表5可见，采用8％β-环糊精键合的-甲基聚硅氧烷色谱柱直接柴油芳烃样品，萘类化合物与部分芳烃化合物共流出，造成分析结果偏高。
实施例3
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某石化加氢柴油作为分析样品。进样口温度为300℃，进样量为1μL，分流比为80:1。第一色谱柱2为3％苯基的二甲基聚硅氧烷的色谱柱，规格30m×0.32mm×0.25μm，流量为0.8mL/min。中心切割组件3的阀切换时间为12.5min打开，14.5min关闭；15.5min打开，18.5min关闭。第二色谱柱4为固定相优选添加15％β-环糊精键合的-甲基聚硅氧烷，规格为60m×0.32mm×0.5μm，柱流量为2mL/min。所述第三色谱柱6为钝化无固定相的空管柱，规格为3.0m×0.15mm，柱流量为2mL/min。第一检测器5为氢火焰离子化检测器，第二检测器7为放空(不接检测器)。色谱系统采用氮气做载 气，程序升温操作，程序升温条件的初温为120℃，以一阶升温速度为3℃/min升温至150℃，然后以2℃/min升温至190℃，恒温10min。
通过标准加入法配置1-甲基萘浓度为10.0％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表6。整个色谱定量分析过程1h。采用相同色谱条件，重复分析外标样品和待测柴油样品1次，考察方法的重复性，结果见表6。
表6 多维色谱法分析加氢柴油萘类化合物含量结果
从表6可见，两次分析结果的最小相对误差为0.62％，最高为5.86％，说明本方法的重复性较好。
以1-甲基萘加标回收率考察本方法的准确性。再取两份某石化加氢柴油样品，其中一份加入53.65mg/kg的2-甲基萘作为加标样品。两份样品均按照前述多维分析方法分别测定1-甲基萘的含量。加标样品中1-甲基萘含量减去未加标样品1-甲基萘含量，其差值同加入的1-甲基萘的理论值之比即为加标回收率，其值为101.2％。由此可见，本方法测定样品的加标回收率较高，说明方法的准确性好。
实施例4
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某石化焦化柴油作为分析样品。进样口温度为310℃，进样量为0.2μL，分流比为200:1。第一色谱柱2为4％苯基的二甲基聚硅氧烷的色谱柱，规格25m×0.32mm×0.25μm，流量为1.5mL/min。中心切割组件3的阀切换时间为12.3min打开，14.3min关闭；16.5min打开，19min关闭。第二色谱柱4为固定相优选添加20％β-环糊精键合的甲基聚硅氧烷，规格为50m×0.53mm×1μm，柱流量为3mL/min。所述第三色谱柱6为钝化无固定相的空管柱，规格为2.5m×0.25mm，柱流量为3mL/min。第一检测器5为氢火焰离子化检测器，第二检测器7为氢火焰离子化检测器。色谱系统采用氮气做载气，程序升温操作，程序升温条件的初温为90℃，以一阶升温速度为2℃/min升温至140℃，然后以0.5℃/min升温至180℃，恒温10min。
通过标准加入法配置2-甲基萘浓度为6.32％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表7。整个色谱定量分析过程1h。
表7 多维色谱法分析焦化柴油萘类化合物含量结果
实施例5
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某公司费托合成柴油作为分析样品。进样口温度为300℃，进样量为0.5μL，分流比为100:1。第一色谱柱2为2％苯基的二甲基聚硅氧烷的色谱柱，规格40m×0.25mm×1μm，流量为1.5mL/min。中心切割组件3的阀切换时间为12.1min打开，14.4min关闭；16.1min打开，19.3min关闭。第二色谱柱4为固定相优选添加11％β-环糊精键合的-50％苯基-甲基聚硅氧烷，规格为20m×0.25mm×1μm，柱流量为4mL/min保持20min后以20mL/min2降至2.0mL/min保持至分析结束。所述第三色谱柱6为钝化无固定相的空管柱，规格为0.50m×0.1mm，柱流量为4mL/min保持20min后以20mL/min2降至2.0mL/min保持至分析结束。第一检测器5为氢火焰离子化检测器，第二检测器7为氢火焰离子化检测器。色谱系统采用氦气做载气，程序升温操作，程序升温条件的初温为80℃，以一阶升温速度为1.5℃/min升温至130℃，然后以0.5℃/min升温至170℃，恒温5min。
通过标准加入法配置1-甲基萘浓度为0.18％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表8。整个色谱定量分析过程1h。
表8 多维色谱法分析费托合成柴油萘类化合物含量结果

实施例6
本实施例提供一种利用多维气相色谱系统分析馏分中萘类化合物的方法，具体如下：
取某公司混合芳烃作为分析样品。进样口温度为300℃，进样量为0.5μL，分流比为100:1。第一色谱柱2为0％苯基的二甲基聚硅氧烷固定相的色谱柱，规格20m×0.53mm×0.25μm，流量为1.5mL/min。中心切割组件3的阀切换时间为12min打开，14min关闭；16min打开，20min关闭。第二色谱柱4为固定相优选添加11％β-环糊精键合的(10％-氰丙基-30％苯基)-甲基聚硅氧烷，规格为40m×0.25mm×0.25μm，柱流量为4mL/min。所述第三色谱柱6为钝化无固定相的空管柱，规格为1.0m×0.1mm，柱流量为4mL/min。第一检测器5为氢火焰离子化检测器，第二检测器7为氢火焰离子化检测器。色谱系统采用氦气做载气，程序升温操作，程序升温条件的初温为80℃，以一阶升温速度为1.5℃/min升温至130℃，然后以0.5℃/min升温至170℃，恒温5min。
通过标准加入法配置1-甲基萘浓度为6.89％的柴油溶液作为外标溶液。采用相同色谱条件分析外标样品和待测柴油样品，分析结果见表9。整个色谱定量分析过程1h。
表9 多维色谱法分析混合芳烃萘类化合物含量结果

对比例4
本对比例提供一种馏分中萘类化合物的分析方法，具体如下：
采用CN1344930A具体实施方式所述方法分析实施例6中样品，色谱条件如下：色谱柱固定相聚二甲基硅氧烷，规格为60m×0.25mm×0.5μm，氦气做载气，程序升温操作，初始温度100℃，然后以5℃/min的升温速率升到130℃，停留10min，再以15℃/min的升温速率升到200℃，停留15min，最后以20℃/min的升温速率升到280℃，停留30min；汽化室温度为250℃，进样口温度为300℃，分流比为100∶1，柱前压为138kPa。分析结果见表10。
表10 一维色谱法分析催化柴油萘类化合物含量结果
由表10可见，采用CN1344930A方法无法实现萘类化合物的基线分离，部分烃类化合物与萘类化合物共流出，造成分析结果偏高。

Claims (17)

  1. 一种利用多维气相色谱系统分析馏分中萘类化合物的方法，其包括如下步骤：
    S1：使待测样品经所述多维气相色谱系统分的进样口进入第一色谱柱，分离出萘类化合物和其他烃类化合物；在中心切割组件控制下，所述萘类化合物进入第二色谱柱，然后进入第一检测器进行分析，得到样品检测图谱；其中，所述第一色谱柱的固定相为苯基含量为0-5％的二甲基聚硅氧烷，所述第二色谱柱的固定相为添加5％-20％β-环糊精键合的-甲基聚硅氧烷；
    S2：将所述样品检测图谱与在相同色谱条件下得到萘类化合物标准品保留时间对比，进行定性分析；
    S3：在相同色谱条件下分析萘类化合物的外标溶液，根据外标法对样品中萘类化合物进行定量分析。
  2. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述第一色谱柱的柱长为20-60m，内径为0.25-0.32mm，流量为0.8-2mL/min。
  3. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述第二色谱柱的柱长为20-60m，内径为0.20-0.53mm，流量为2-4mL/min。
  4. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，S1还包括：在中心切割组件控制下，所述其他烃类化合物进入第三色谱柱，然后进入第二检测器进行分析。
  5. 根据权利要求4所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述多维气相色谱系统中，进样口与第一色谱柱的入口连通，第一色谱柱的出口与中心切割组件的入口连通；所述中心切割组件的第一出口与第二色谱柱的入口连通，第二色谱柱的出口与第一检测器连通；所述中心切割组件的第二出口与第三色谱柱的入口连通，第三色谱柱的出口与第二检测器连通。
  6. 根据权利要求5所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述中心切割组件还包括：微流控组件、载气入口、阻尼柱和电磁阀；
    其中，所述微流控组件包括第一端口、第二端口和第三端口；所述第一端口形成为所述中心切割组件的入口，所述第二端口与所述中心切割组件的第一出口连通，所述第三端口与所述中心切割组件的第二出口连通；
    所述中心切割组件具有可切换的第一工作状态和第二工作状态；在所述第一工作状态，所述电磁阀处于关闭状态，所述载气入口通过第一载气管路与所述中心切割组件的第二出口连通，用于使载气通过第一载气管路、所述中心切割组件的第二出口与流出第 一色谱柱的组分一起进入第三色谱柱；
    在所述第二工作状态，所述电磁阀处于开启状态，所述载气入口通过第二载气管路与所述中心切割组件的第一出口连通，用于使所述载气通过第二载气管路、所述中心切割组件的第一出口与流出第一色谱柱的组分一起进入所述第二色谱柱。
  7. 根据权利要求6所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述中心切割的电磁阀的切换时间为12-12.5min打开，14-14.5min关闭；15.5-16.5min打开，18.5-20min关闭。
  8. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述进样口的温度为280-310℃，进样量为0.1-1μL，分流比为80:1-250:1。
  9. 根据权利要求4所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述第三色谱柱为钝化无固定相的空管柱，第三色谱柱阻力与所述第二色谱柱相同，柱长为0.5-3.0m，内径为0.10-0.32mm，柱流量为2-4mL/min。
  10. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述第一检测器为氢火焰离子化检测器。
  11. 根据权利要求4所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述第二检测器为热导检测器、氢火焰离子化检测器或是直接放空。
  12. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，多维气相色谱系统所用载气为氦气或氮气；
    采用程序升温操作，程序升温条件包括：初温为80-120℃，一阶升温速度为1-3℃/min，升温至130-150℃，二阶升温速度为0.5-2℃/min，升温至170-190℃，恒温5-20min。
  13. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述外标溶液选自萘、1-甲基萘或2-甲基萘的标准品溶液，其浓度范围为0.1wt％-10wt％。
  14. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述萘类化合物包括萘、甲基萘、二甲基萘中的一种或多种。
  15. 根据权利要求14所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述萘类化合物包括萘、1-甲基萘、2-甲基萘、2-乙基萘、1-乙基萘、2,6-二甲基萘、2,7-二甲基萘、1,7-二甲基萘、1,3-二甲基萘、1,6-二甲基萘、1,4-二甲基萘、1,5-二甲基萘、2,3-二甲基萘、1,2-二甲基萘、1,8-二甲基萘中的一种或多种。
  16. 根据权利要求1所述的利用多维气相色谱系统分析馏分中萘类化合物的方法， 其中，所述馏分包含160-400℃馏分中的至少一种馏分。
  17. 根据权利要求16所述的利用多维气相色谱系统分析馏分中萘类化合物的方法，其中，所述馏分包含200-250℃馏分中的至少一种馏分。
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