WO2023065811A1 - Procédé de mesure de teneur en méthanol dans une huile essentielle de bille à éclater de cigarette - Google Patents

Procédé de mesure de teneur en méthanol dans une huile essentielle de bille à éclater de cigarette Download PDF

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Publication number
WO2023065811A1
WO2023065811A1 PCT/CN2022/114449 CN2022114449W WO2023065811A1 WO 2023065811 A1 WO2023065811 A1 WO 2023065811A1 CN 2022114449 W CN2022114449 W CN 2022114449W WO 2023065811 A1 WO2023065811 A1 WO 2023065811A1
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WO
WIPO (PCT)
Prior art keywords
methanol
headspace
essential oil
cigarettes
signal value
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PCT/CN2022/114449
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English (en)
Chinese (zh)
Inventor
王浩
郑晗
詹建波
余振华
张莹
谢姣
王涛
余婷婷
王旭
岳保山
余耀
程量
余江
李利伟
丁海燕
丁卫
张静
桂永发
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云南中烟工业有限责任公司
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Publication of WO2023065811A1 publication Critical patent/WO2023065811A1/fr

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/64Electrical detectors
    • G01N30/68Flame ionisation detectors

Definitions

  • the invention relates to the technical field of detection of methanol content, in particular to a method for accurately measuring the content of methanol in popcorn essential oil for cigarettes by using full vaporization headspace gas chromatography.
  • Methanol is an important organic raw material and is widely used in industry. Methanol is highly toxic. Once ingested by the human body, it will be metabolized into formic acid and formate that are harmful to the central nervous system. In severe cases, it will cause blindness, coma or even death. Therefore, in food, drinking water and air, the concentration of methanol has strict restrictions and must be below 5-10mg/kg.
  • Popcorn essential oil for cigarettes is an important food additive. A large amount of chemical solvents such as ethanol, propylene glycol, and petroleum ether are used in the process of dissolution, extraction, and synthesis. These residual methanol may be brought into food. And then pose a serious threat to human health. In view of this, it is necessary to establish a rapid and accurate method for the determination of residual methanol content in popcorn essential oil for cigarettes, which has an important guiding role in ensuring food quality and reducing safety risks.
  • the detection methods of the methanol content in the popcorn essential oil (oil phase) for cigarettes are mainly gas chromatography and high performance liquid chromatography.
  • gas chromatography since the popcorn essential oil system for cigarettes contains high-boiling solvents such as caprylic acid glyceride (boiling point is 456 ° C), direct sampling detection will pollute the sampling system, and then affect the service life of the instrument; therefore, in order to reduce Risk, pretreatment steps such as extraction and separation with organic solvents are required before detection. These pretreatments are not only cumbersome and inefficient, but also affect the accuracy of detection results.
  • Raman spectroscopy, infrared spectroscopy, and ultraviolet-visible spectroscopy are based on the determination of the characteristic peaks of the characteristic functional groups (methyl) in methanol to determine the methanol content.
  • the main problem is that it will be affected by the complex matrix of the sample and the detection sensitivity is not high.
  • the principle of spectrophotometric method for measuring methanol is to oxidize methanol into formaldehyde, and formaldehyde reacts with chromogenic agents such as sulfite fuchsin, chromotropic acid, etc.
  • the present invention is proposed to solve the above-mentioned problems.
  • the present invention provides a method for accurately measuring the content of methanol in popcorn essential oil system for cigarettes by using full vaporization headspace gas chromatography.
  • the method of the invention has the advantages of fast detection speed, high result accuracy, simple and convenient operation, etc., and overcomes the disadvantages existing in the current determination of the methanol content in the oil phase system.
  • the present invention adopts full-vaporization headspace gas chromatography to measure the methanol content in the popcorn essential oil for cigarettes.
  • the specific principle is: in a closed headspace bottle, when the equilibrium temperature of the headspace exceeds the boiling point of methanol, The methanol will be completely transferred from the liquid phase to the gas phase; the signal value of methanol is determined based on full vaporization headspace gas chromatography, and then the methanol content in the popcorn essential oil for cigarettes is calculated through the standard curve.
  • the present invention realizes through following technical scheme:
  • a method for accurately measuring the content of methanol in the popcorn essential oil for cigarettes by full-vaporized headspace gas chromatography comprising the steps of:
  • the puffed pearl essential oil for cigarettes into a headspace bottle after ultrasonic treatment and seal it;
  • the conditions for ultrasonic treatment are preferably: 400w, time: 5min;
  • the puffed pear essential oil for cigarettes can be liquid;
  • step 2 Place the headspace vial of step 1 in the headspace sampler, and measure the signal value of methanol in the headspace vial by full vaporization headspace gas chromatography;
  • the eluting time of the methanol peak is 0.668 min.
  • the conditions of the headspace sampler in step 2 are as follows: the initial equilibrium temperature is 105°C, the equilibrium time is 2min; The time to GC is 20s; the maximum injection volume is 40 ⁇ L.
  • gas chromatography operating conditions in step 2 hydrogen flame ion detector, carrier gas is nitrogen, flow rate is 25mL/min; combustible gas is hydrogen, flow rate is 30mL/min; assisted gas is oxygen, flow rate is 400mL/min;
  • the detector temperature is 250°C, the split ratio is 2:1, and the detection time is 2min.
  • A is -157.66 ⁇ 21.91; B is 83.99 ⁇ 0.9197.
  • the method of the present invention utilizes full-vaporized headspace gas chromatography to measure the methanol content in the popcorn essential oil for cigarettes for the first time.
  • the detection method of the invention is easy to operate and has high precision; the limit of quantification of methanol detection in the popcorn essential oil for cigarettes can reach 0.73 mg/mL.
  • the detection method of the invention can detect in batches, thereby improving the efficiency; it overcomes the disadvantages of low detection sensitivity, cumbersome operation, low time-consuming efficiency, high organic solvent loss and the like in the prior art method.
  • the method of the present invention utilizes full-vaporized headspace gas chromatography to accurately measure the methanol content in the popcorn essential oil for cigarettes, avoids the influence of high-boiling solvents on the measurement results during direct sample injection, and has a wide range of applications.
  • the method of the present invention can accurately quantitatively analyze the methanol content in the popcorn essential oil for cigarettes, provide guidance for the determination of the methanol content in the oil phase, and play an important guiding role in ensuring food quality and reducing safety risks.
  • Fig. 1 is the gas chromatogram of the volatile target substance in the popcorn essential oil for smoking with the temperature of the chromatographic column being 60°C.
  • Figure 2 is a graph showing the effect of headspace equilibration time on methanol signal value.
  • Fig. 3 is a graph showing the effect of the headspace equilibrium temperature on the methanol signal value.
  • Equipment and reagents used DANI HS 86.50 PLUS, Italy type automatic headspace sampler, Agilent GC 8860, US type gas chromatograph (hydrogen flame ion detector, GS-Q type capillary column), headspace bottle ( 20.0ml), blue Teflon/blue silicone septa (with aluminum cap).
  • the headspace sampler conditions were as follows:
  • the equilibrium temperature is 105°C
  • the equilibrium time is 2min
  • the pressurization time of the headspace bottle is 15s
  • the depressurization time is 15s
  • the filling time of the quantitative loop is 10s
  • the transfer line time is 20s
  • the injection purge time is 20s
  • the pressurization pressure is 1bar.
  • the inlet pressure is 22.47psi
  • the inlet temperature is 250°C
  • the split ratio is 2:1
  • the detector temperature is 250°C
  • the detection time is 2min
  • the hydrogen flow rate is 30mL /min
  • the oxygen flow rate of the assisted gas is 400mL/min
  • the make-up flow is 25mL/min
  • the detector temperature is 250°C.
  • FIG. 1 is a gas chromatogram of a sample of cigar bead extract when the oven temperature is 60°C. It can be seen from Figure 1 that methanol and other volatile substances can be better separated at a lower oven temperature, and the methanol retention time is 0.668min. Therefore, the temperature of the chromatographic column selected in the present invention is 60°C.
  • A is the GC signal value (ie peak area) of methanol in the headspace vial
  • C is the concentration of methanol in the standard solution (unit: mg/mL).
  • the limit of quantitation (LOQ) of methanol detection by this method can be calculated by the following formula:
  • a, s, and ⁇ a are the intercept, slope, and standard deviation of the intercept in formula (1), respectively. From the formula (2), it can be calculated that the quantitative limit of the method for the detection of methanol in the popcorn essential oil for cigarettes is 0.73 mg/mL.
  • the reproducibility evaluation of the method of the present invention is to carry out 3 repeated experiments on 4 different paper samples, and compare the detection results to obtain the relative standard deviation value of the detection results.
  • the reproducibility test results of the method of the present invention are shown in Table 2. It can be seen from Table 2 that the relative standard deviations of the method for different samples of popcorn essential oil for cigarettes are all less than 3.89%. Therefore, it can be considered that the method of the present invention has good reproducibility for detecting residual methanol in the popcorn essential oil for cigarettes.
  • the accuracy evaluation of the method of the present invention is to add 10-80 ⁇ L of pure methanol solution to 10mL sample (methanol content in the sample is 1.94mg/mL), respectively, to obtain a spiked sample solution.
  • the non-spiked popcorn essential oil sample with a methanol content of 1.94 mg/mL was used as a reference object to detect the net contribution of the added standard, and the results are shown in Table 3. It can be seen from Table 3 that the recovery rate of the method of the present invention for detecting the methanol content in the popcorn essential oil for cigarettes is between 97.8% and 101%, which shows that the method has good accuracy.
  • the method of the present invention can accurately quantitatively analyze the methanol content in the popcorn essential oil for cigarettes; the detection method is easy to operate and has high precision.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

Procédé de mesure de la teneur en méthanol dans une huile essentielle de bille à éclater de cigarette à l'aide d'un procédé de chromatographie en phase gazeuse d'espace de tête entièrement vaporisé, comprenant les étapes suivantes consistant : (1) après soumission de l'huile essentielle de bille à éclater de cigarette à un traitement par ultrasons, à mettre en place l'huile essentielle de bille à éclater de cigarette dans une bouteille d'espace de tête et à refermer hermétiquement ; (2) à mettre en place la bouteille d'espace de tête de l'étape (1) dans un injecteur d'échantillon d'espace de tête, et à mesurer une valeur de signal du méthanol dans la bouteille d'espace de tête au moyen d'un procédé de chromatographie en phase gazeuse d'espace de tête entièrement vaporisé ; et (3) à substituer la valeur de signal du méthanol obtenu à l'étape (2) dans une courbe standard afin d'obtenir la teneur en méthanol dans l'huile essentielle de bille à éclater de cigarette. L'effet bénéfique est que le procédé de mesure est simple et pratique à utiliser et d'une grande précision.
PCT/CN2022/114449 2021-10-22 2022-08-24 Procédé de mesure de teneur en méthanol dans une huile essentielle de bille à éclater de cigarette WO2023065811A1 (fr)

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CN202111232950.3A CN113960229A (zh) 2021-10-22 2021-10-22 一种烟用爆珠精油中甲醇含量的测定方法
CN202111232950.3 2021-10-22

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CN113960229A (zh) * 2021-10-22 2022-01-21 云南中烟工业有限责任公司 一种烟用爆珠精油中甲醇含量的测定方法

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