CN110850010B - Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke - Google Patents
Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke Download PDFInfo
- Publication number
- CN110850010B CN110850010B CN201911109247.6A CN201911109247A CN110850010B CN 110850010 B CN110850010 B CN 110850010B CN 201911109247 A CN201911109247 A CN 201911109247A CN 110850010 B CN110850010 B CN 110850010B
- Authority
- CN
- China
- Prior art keywords
- filter stick
- temperature
- purging
- benzene series
- cigarette
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Landscapes
- 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)
Abstract
The invention relates to a simulation determination method for migration of benzene series in a cigarette filter stick to cigarette smoke, and belongs to the technical field of analytical chemistry. The device provided by the invention is adopted to simulate real smoking of cigarettes to purge the filter stick, the adsorption cold trap is used for trapping the purged benzene series, the content of the benzene series components is measured through a gas chromatography-mass spectrum connected with a dynamic headspace after trapping is finished, and then the mobility is calculated. The method can meet the requirement of accurately measuring the benzene series in the cigarette filter stick to the cigarette smoke migration quantity, and provides a scientific, simple and convenient new method for objectively evaluating the benzene series residue safety of the cigarette filter stick.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a simulation determination method for benzene series migration in a cigarette filter stick to cigarette smoke.
Background
The cigarette filter stick is a tool specially designed for smokers, and can reduce smoke, tar and suspended particles generated during combustion when the cigarette is smoked. And (3) the interception function on particulate matters and harmful components of cigarette smoke. In recent years, in order to reduce harm and tar and highlight the personalized style of cigarette products, the application of a new material capable of realizing specific effects in a filter tip to highlight the characteristics of the cigarette products becomes a new technological innovation hotspot. The cigarette product researchers aim at expanding consumer groups, and the developed cigarette products realize the effects of reducing harm and tar, enhancing the pleasure, comfort and satisfaction of consumers and the like by adding new materials such as blasting beads, particles, aromatic threads and the like into the filter tips. New filter tip materials such as exploded beads, particles, aromatic threads and the like are increasingly applied to more cigarette brands at home and abroad, and the filter tip materials show a trend of being developed and applied to the dominant brands of various enterprises in recent two years.
Because a plurality of chemical raw materials are used in the processing and production process of the traditional acetate fiber filter stick of the cigarette, if the monitoring is neglected, the residual benzene series substances can be brought into the filter stick, thereby bringing safety risk to the filter stick. On the other hand, various novel filter sticks are increasingly applied to cigarettes, and fillers, functional additives, coloring agents, core essences and coating materials used by various companies in the filter sticks are different; the use of a large amount of new materials also can introduce benzene series, and bring new safety risks to cigarette products.
At present, benzene series is a project for frequently detecting tobacco materials (paper, filter sticks) and tobacco additives (essence) in the tobacco industry in China. The benzene solvent can cause the cigarette to generate bad smell, and the benzene solvent can cause the harm of carcinogenesis, teratogenesis, mutation and the like to human bodies. The tobacco industry has requirements and limitations on residual benzene solvents for both tobacco materials and tobacco additives. In the currently reported method for detecting benzene series in cigarette filter sticks, the content in the filter sticks is mainly measured, and the mobility of the benzene series in the cigarette smoke is not considered. For cigarette products, only the part migrating to cigarette smoke can act with human bodies, so that the evaluation of the benzene series residue safety in the filter stick on the basis of considering the migration rate is more in line with the reality of the cigarette products.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for simulating and measuring the benzene series in the cigarette filter stick to the cigarette smoke, which can meet the requirement of accurately measuring the benzene series migration amount in the filter stick and provides a scientific, simple and convenient new method for evaluating the safety of the benzene series residue in the filter stick.
All percentages used herein are by weight unless otherwise indicated.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
the device comprises an airflow preheating cavity, a numerical control three-way valve, a purging pipe and a dynamic headspace gas chromatography-mass spectrometry instrument;
the numerical control three-way valve is arranged between the airflow preheating cavity and the purging pipe;
the gas outlet of the purging pipe is connected with a dynamic headspace gas chromatography-mass spectrometry instrument;
the airflow preheating cavity is connected with an air inlet of the numerical control three-way valve;
the airflow preheating cavity is a quartz glass tube, and the gas in the tube is preheated by adopting infrared radiation;
the method comprises the following steps:
step (1), gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and sweep the filter stick, when suction is simulated, air flow enters a sweeping pipe and is communicated with the filter stick, and when static combustion is simulated, the air flow directly enters the atmosphere; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, an ISO standard suction mode or a Canadian deep suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic spectrum are as follows: the desorption time is 2-5min, the desorption temperature is 220-250 ℃, the transmission line temperature is 250-280 ℃, and the valve box temperature is 250-280 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
Further, it is preferable that the purge pipe includes a pipe body and a pipe cap; the pipe body is connected with the pipe cap; two sealing rings which are used for fixing the filter stick and only allow air flow to pass through the filter tip are arranged in the tube body, and the two sealing rings are respectively arranged at two ends of the filter stick. The sealing ring can realize the sealing between the filter stick and the blowing pipe wall, avoid the side of blowing air flow to pass through and ensure the air flow to pass through the filter stick. By adjusting the size and the position of the sealing ring up and down, the requirements of filter tip tests of all specifications of cigarettes can be met, such as conventional cigarettes, medium cigarettes, thin cigarettes, long filter cigarettes, short filter cigarettes and the like, as shown in figure 3.
The air flow preheating cavity is arranged to realize the programmed temperature rise of the air in the cavity, so that the temperature of the air flow passing through the filter stick is consistent with the actual sweeping temperature of the cigarette smoke.
The numerical control three-way valve can realize automatic switching, can simulate the standard smoking condition of a smoking machine, the air flow is not communicated with the filter rod when the cigarette is in a static combustion state and is directly discharged to the outside, and the air flow is communicated with the filter rod to purge the bead blasting filter rod when the cigarette is in a smoking state.
Further, in the step (1), preferably, the filter stick is purged by simulating an ISO standard suction mode, the purging is continued for 2 seconds every 1 minute, and the flow rate of the purging air flow is 17.5 mL/min; the Canadian deep suction mode is simulated to purge the filter stick, the purging lasts for 2 seconds every 30 minutes, and the flow rate of the purging airflow is 22.5mL/min; purging for 8-10 times.
Namely, the method simulates an ISO standard suction mode to purge the filter stick, and simulates 2s cigarette suction time, and the process is as follows: through the switching of a numerical control three-way valve, airflow enters from an air inlet of the numerical control three-way valve and then enters a purging pipe from one air outlet to purge and elute the exploded beads in the filter stick, wherein the purging time is 2s; then, simulating the static burning time of the 58s cigarette, and the process is as follows: through the switching of the numerical control three-way valve, the air flow enters from the air inlet of the numerical control three-way valve and then enters the atmosphere from the other air outlet without passing through the filter rod.
Purging 8-10 times, namely simulating 8-10 mouths of suction.
Further, it is preferable that, in the step (2), the adsorption material of the trap is silica gel particles (bona aiger company) coated with poly (methyl-3, 5-trifluoropropylsiloxane), which has a large adsorption capacity for cooling agent components, good stability at high temperature, reversible adsorption and desorption, and can be reused many times. The trap temperature was-20 ℃.
Further, it is preferable that, in the step (2), the gas chromatography conditions are as follows: the chromatographic column is a VOC special capillary column (VOCOL column or equivalent column), and has the specification of 60m in length, 0.32mm in inner diameter and 1.8 μm in film thickness; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 6 min; heating to 100 ℃ at a heating rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
Further, it is preferable that, in the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is electron impact source (EI), the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
Further, it is preferable that, in the step (2), the method of calculating the mobility is: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility; mobility = (peak area simulating actual pumping measurement/peak area of total amount) × 100%.
When the measurement of actually sucked benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using not less than 10 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8-15min by using gas at 160-200 ℃, continuously purging the new filter stick again after purging, purging not less than 10 filter sticks (the number of the filter sticks is the same as that of the filter sticks adopted during measurement of simulated actually pumped benzene series components), and then measuring the total benzene series components. The total amount measurement trapping, desorption, GC and MS conditions are completely the same as the conditions for simulating the measurement of the amount of the actually pumped benzene series components.
This is because the benzene-based component migrates only a small amount, and in order to reach the limit of quantitation of the apparatus, at least 10 filter rods are purged cumulatively.
When the heating program is set, cigarettes of different specifications are actually smoked on the smoking machine, the actual temperature of smoke passing through the filter stick is measured by the thermocouple, and then the setting is carried out according to the measurement result.
The ion selection parameter principle of the invention is as follows: selecting ions with higher specificity and response from mass spectrum ion fragments of each solvent residue as quantitative ions; and selecting other 1 to 2 fragment ions as auxiliary qualitative ions. The ion selection parameters are shown in table 1. A typical chromatogram is shown in FIG. 4.
TABLE 1 quantitative and qualitative ion selection for benzene series
Further, in order to quantitatively analyze the benzene series component, it is preferable that 25, 10, 5, and 2 kinds of cooling agent controls are used in the present invention. 5. Solutions were prepared from six concentration levels of 1.0 and 0.1 mg/mL of mixed standard working solutions inAnd injecting 1.0 mu L sample under the preferable chromatographic condition to prepare a working curve, wherein the cooling agent components entering the chromatographic system are respectively 25, 10, 5, 2.5, 1.0 and 0.1 mu g. Taking the response value (chromatographic peak) of the quantitative ions of the cooling agent as the ordinate Y value, and taking the benzene series concentration (C:)µg) The abscissa X represents the value of the working curve, which is shown in Table 2. And the quantitative analysis of the components of the transferable cooling agent can be realized according to the comparison of the chromatographic peak signal of the sample to be detected and the working curve.
Working curves of 7 benzene series shown in Table 2
Compared with the prior art, the invention has the following beneficial effects:
(1) The method comprehensively considers the transfer of benzene compounds in the cigarette filter stick to the cigarette smoke, and overcomes the problems that the total content in the filter stick is mainly measured and the transfer of the benzene compounds to the cigarette smoke is not considered in the traditional filter stick benzene compound detection method. The migration amount is comprehensively considered, and the evaluation on the benzene series residue safety can better accord with the reality of cigarette products.
(2) The device adopted by the invention has simple structure and easy operation. Compared with the direct analysis of the cigarette smoke, the interference of the complex background generated by the cigarette combustion on the measurement of the benzene series can be deducted; the whole analysis process is on-line operation, so that errors caused by multiple sample transfer in other methods are avoided, and the benzene series measurement result is more accurate and reliable; compared with other simulation transfer devices, the device provided by the invention simulates the actual situation closer to cigarette smoking, and the obtained result is more objective and reliable.
(3) According to the invention, the precise purging tube is adopted, the purging tube is of a ferrule type structure with a sealing ring, the sealing ring can realize sealing between the filter rod and the purging tube wall, and the side edge of purging airflow is prevented from passing (the airflow is ensured to pass through the filter rod). The requirements of testing filter sticks (conventional cigarettes, medium cigarettes, thin cigarettes, long filter cigarettes, short filter cigarettes and the like) with all specifications of cigarettes can be met by adjusting the size and the position (up and down) of the sealing ring.
(4) The invention also adopts silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane) as the adsorption material of the trap for the first time. The material has large adsorption capacity, good stability at high temperature, good reversibility of adsorption and desorption of the benzene series compound, high completeness of adsorption and desorption of the component to be detected, and can obviously improve the accuracy and precision of an analysis result.
Drawings
FIG. 1 is a schematic diagram of the structure of an apparatus used in the present invention;
FIG. 2 is an exploded view of the purge tube;
wherein, 1, an air flow preheating cavity is formed; 2. a numerical control three-way valve; 3. a purge tube; 3-1, a pipe body; 3-2, a pipe body; 3-3, sealing rings; 4. a dynamic headspace gas chromatography-mass spectrometry instrument; 5. filtering the filter stick; 5-1, an upper filter rod core; 5-2, lower filter stick core; 5-3, tipping paper; 6. bead blasting;
FIG. 3 is a schematic view of different types of cigarette filter rods installed in the purge tube; wherein a is a filter stick of a conventional cigarette, b is a filter stick of a fine cigarette, and c is a filter stick of a short filter cigarette;
FIG. 4 is a detection chromatogram
Wherein, 1-benzene, 2-toluene, 3-ethylbenzene, 4-para-xylene, 5-meta-xylene, 6-ortho-xylene and 7-styrene.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.
Example 1
A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The method comprises the following steps:
step (1), purging with gas flow: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, an ISO standard suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic chromatography are as follows: the desorption time is 2min, the desorption temperature is 250 ℃, the transmission line temperature is 250 ℃, and the valve box temperature is 250 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; purging 8 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃, and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and has the specification of 60m in length, 0.32mm in inner diameter and 1.8 μm in film thickness; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature-raising program is: maintaining the initial temperature of 40 ℃ for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually pumped benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using 10 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 5min by using gas at 160 ℃, continuously purging the filter stick by replacing the new filter stick again after purging is finished, purging 10 filter sticks in total, and then measuring the total benzene series components.
The test cigarette filter stick is a conventional cigarette flavoring filter stick with the specification of 30 mm. And (4) taking the filter stick from the cigarette, and filling the filter stick into a purging pipe for measurement.
The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
Example 2
A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the air flow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of the suction openings of the cigarettes is simulated;
when a smoking machine is simulated to suck and purge the filter stick, an ISO standard suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic chromatography are as follows: the desorption time is 5min, the desorption temperature is 220 ℃, the transmission line temperature is 280 ℃, and the valve box temperature is 280 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; purging was performed 9 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃ and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and has the specification of 60m in length, 0.32mm in inner diameter and 1.8 μm in film thickness; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
Mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually sucked benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using 15 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and (3) replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8min by using 1200 ℃ gas, continuously purging the filter stick by replacing the new filter stick again after purging is finished, purging 15 filter sticks in total, and then measuring the total benzene series components.
The test cigarette filter stick is a conventional cigarette gel flavor-carrying filter stick with the specification of 30 mm. And (4) taking the filter stick from the cigarette, and filling the filter stick into a purging pipe for measurement.
The measurement result shows that: styrene is detected in the sample, and the total content is 0.485µg/branch, the migration amount is 351.2 ng/branch, and the mobility is 7.24 percent respectively.
Compared with the condition that the content of the styrene in the food contact material is less than 0.5 mg/g specified in GB 9685-2016 (Standard for use of food contact materials and additives for products), the residual transferable amount of the styrene in the filter stick does not bring safety risk to cigarette products.
Example 3
A simulation determination method for benzene series substance in a cigarette filter stick to migrate to cigarette smoke adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the air flow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The air flow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, an ISO standard suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic chromatography are as follows: the desorption time is 2.5min, the desorption temperature is 230 ℃, the transmission line temperature is 260 ℃, and the valve box temperature is 270 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; purging 10 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃, and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and the specification is that the length is 60m, the inner diameter is 0.32mm, and the film thickness is 1.8 mu m; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature-raising program is: maintaining the initial temperature of 40 ℃ for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually sucked benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using not less than 10 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 10min by using gas at 180 ℃, continuously purging the filter stick again by replacing the new filter stick after purging, purging not less than 10 filter sticks in total, and then measuring the total benzene series components.
The test cigarette filter stick is a conventional cigarette bead blasting filter stick with the specification of 25 mm. And taking the filter stick from the cigarette, pinching the blasting beads, and filling the blasting beads into a purging tube for measurement. The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
Example 4
A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating chamber 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The air flow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and sweep the filter stick, when suction is simulated, air flow enters a sweeping pipe and is communicated with the filter stick, and when static combustion is simulated, the air flow directly enters the atmosphere; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and sweep the filter stick, an ISO standard suction mode is simulated to sweep the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic spectrum are as follows: the desorption time is 3.5min, the desorption temperature is 240 ℃, the transmission line temperature is 260 ℃, and the valve box temperature is 260 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; purging was performed 9 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃, and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and the specification is that the length is 60m, the inner diameter is 0.32mm, and the film thickness is 1.8 mu m; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature-raising program is: maintaining the initial temperature at 40 deg.C for 6 min; heating to 100 ℃ at a heating rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actually pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually pumped benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using 10 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 10min by using gas at the temperature of 180 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 10 filter sticks in total, and then measuring the total amount of the benzene series components.
The test cigarette filter stick is a conventional cigarette filter stick added with particles, and the specification is 25 mm. And (4) taking the filter stick from the cigarette, and filling the filter stick into a purging pipe for measurement.
The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
Example 5
A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating chamber 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of the suction openings of the cigarettes is simulated;
when a smoking machine is simulated to suck and sweep the filter stick, an ISO standard suction mode is simulated to sweep the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic chromatography are as follows: the desorption time is 4min, the desorption temperature is 235 ℃, the transmission line temperature is 250-280 ℃, and the valve box temperature is 250-280 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; purging was performed 9 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃ and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and the specification is that the length is 60m, the inner diameter is 0.32mm, and the film thickness is 1.8 mu m; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature of 40 ℃ for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually sucked benzene series components is simulated, replacing a new filter stick after each filter stick is blown, blowing again, and using 12 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 12min by using gas at 190 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 12 filter sticks in total, and then measuring the total amount of the benzene series components.
The test cigarette filter stick is a conventional cigarette filter stick added with flavor threads, and the specification is 30 mm. And taking the filter stick from the cigarette, and placing the filter stick into a purging pipe for determination.
The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
Example 6
A simulation determination method for benzene series substance in a cigarette filter stick to migrate to cigarette smoke adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), purging with gas flow: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, a Canadian deep suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic spectrum are as follows: the desorption time is 3.2min, the desorption temperature is 240 ℃, the transmission line temperature is 250 ℃, and the valve box temperature is 250 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), a Canada deep suction mode is simulated to purge the filter stick, the purging is continued for 2 seconds every 30 seconds, and the flow rate of the purging airflow is 22.5mL/min; purging 8 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃, and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and has the specification of 60m in length, 0.32mm in inner diameter and 1.8 μm in film thickness; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually pumped benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using 20 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 13min by using gas at 170 ℃, continuously purging the filter stick by replacing the new filter stick again after purging is finished, purging 20 filter sticks in total, and then measuring the total benzene series components.
The test cigarette filter stick is a fine cigarette bead blasting filter stick with the specification of 35 mm. And taking the filter stick from the cigarette, breaking the blasting beads by pinching, and filling the filter stick into a purging tube for determination.
The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
Example 7
A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick adopts the following devices:
as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The air flow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), purging with gas flow: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, a Canadian deep suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatographic chromatography are as follows: the desorption time is 2.8min, the desorption temperature is 240 ℃, the transmission line temperature is 270 ℃, and the valve box temperature is 265 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene.
In the step (1), a Canada deep suction mode is simulated to purge the filter stick, the purging is continued for 2 seconds every 30 seconds, and the flow rate of the purging airflow is 22.5mL/min; purging for 8-10 times.
In the step (2), the adsorbing material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane), and the temperature of the trap is-20 ℃. The particle size of the silica gel particles is 100 to 150 meshes; the drying temperature is 200 ℃ and the drying time is 6h.
The gas chromatography conditions were as follows: the chromatographic column is a capillary column special for VOC, and has the specification of 60m in length, 0.32mm in inner diameter and 1.8 μm in film thickness; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature of 40 ℃ for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
The mass spectrometry conditions were as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min. A selective ion monitoring mode is employed.
The method for calculating the mobility comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually pumped benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using 20 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 9min by using gas at the temperature of 170 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 20 filter sticks in total, and then measuring the total amount of the benzene series components.
The filter stick of the test cigarette is a filter stick of a medium cigarette with a bead blasting specification of 25 mm. And taking the filter stick from the cigarette, breaking the blasting beads by pinching, and filling the filter stick into a purging tube for determination.
The determination result shows that no benzene series is detected in the filter stick, and the safety risk caused by the introduction of the benzene series does not exist.
In addition, in order to accurately measure the total amount of benzene series in the filter stick, the filter stick with 7 artificially added benzene series is prepared in the invention, and the adding amount of 7 components in each cigarette filter stick is respectively 2.0µg. After the filter stick is placed in the blowing pipe, the filter stick is continuously blown for 10min at 180 ℃ so that the benzene series in the filter stick can be completely blown out, the total amount of the benzene series is measured by the method of example 1, and the result is shown in Table 3. As can be seen from the results in Table 3, the recovery rates of the measurement results of the 7 benzene series are all more than 87.6%, which shows that the recovery rate of the measurement results of the method is high and the results are reliable. Meanwhile, the filter stick containing the 7 benzene series substances is artificially prepared to simulate real smoking and blowing of the cigarette, the blowing mode is as in example 1, the benzene series substances are measured by the method of example 1, and the detection results are shown in table 3.
TABLE 3
As can be seen from the results in Table 3, the mobility of the 7 benzene-based ester components is between 7.15% and 8.93%. Migration of this type of ingredient does occur, but the proportion of migration is very small, all below 10%. Because the benzene series substances capable of migrating in the cigarette filter stick are likely to react with the human body, the migration amount of the benzene series substances needs to be objectively considered when the residual safety of the benzene series substances in the cigarette filter stick is evaluated.
The migration volume of the same filter stick is subjected to parallel measurement for 5 times, the Relative Standard Deviation (RSD) is 3.5 to 4.2 percent, and the method has good reproducibility and can meet the requirement of accurate measurement of the migration volume of the benzene series.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A simulation determination method for benzene series migration to cigarette smoke in a cigarette filter stick is characterized by comprising the following steps:
the device comprises an airflow preheating cavity, a numerical control three-way valve, a purging pipe and a dynamic headspace gas chromatography-mass spectrometry instrument;
the numerical control three-way valve is arranged between the airflow preheating cavity and the purging pipe;
the gas outlet of the purging pipe is connected with a dynamic headspace gas chromatography-mass spectrometry instrument;
the airflow preheating cavity is connected with an air inlet of the numerical control three-way valve;
the air flow preheating cavity is a quartz glass tube, and the gas in the tube is preheated by adopting infrared radiation;
the method comprises the following steps:
step (1), purging with gas flow: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, the smoking machine is simulated to suck and sweep the filter stick, when suction is simulated, air flow enters a sweeping pipe and is communicated with the filter stick, and when static combustion is simulated, the air flow directly enters the atmosphere; meanwhile, the actual number of suction openings of the cigarette is simulated;
when a smoking machine is simulated to suck and purge the filter stick, an ISO standard suction mode or a Canadian deep suction mode is simulated to purge the filter stick;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, benzene series components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
wherein, the conditions of heating analysis and chromatography are as follows: the desorption time is 2-5min, the desorption temperature is 220-250 ℃, the transmission line temperature is 250-280 ℃, and the valve box temperature is 250-280 ℃;
the benzene series comprises benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene and styrene; the adsorption material of the trap is silica gel particles coated with poly (methyl-3, 5-trifluoropropylsiloxane).
2. The method for simulated determination of benzene series migration to cigarette smoke in a cigarette filter stick according to claim 1, wherein the purging tube comprises a tube body and a tube cap; the pipe body is connected with the pipe cap; two sealing rings which are used for fixing the filter stick and only allow air flow to pass through the filter tip are arranged in the tube body, and the two sealing rings are respectively arranged at two ends of the filter stick.
3. The method for simulating and measuring the migration of the benzene series in the cigarette filter stick to the cigarette smoke according to claim 1, wherein in the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds in every 1 minute, and the flow rate of purge air flow is 17.5 mL/min; the Canadian deep suction mode is simulated to purge the filter stick, the purging lasts for 2 seconds every 30 seconds, and the flow rate of the purging airflow is 22.5mL/min; purging for 8-10 times.
4. The method for simulated measurement of benzene series migration to cigarette smoke in cigarette filter sticks according to claim 1, characterized in that, in the step (2), the temperature of the trap is-20 ℃.
5. The method for simulating and measuring the benzene series migration to the cigarette smoke in the cigarette filter stick according to claim 1, wherein in the step (2), the gas chromatography conditions are as follows: the chromatographic column is a capillary column special for VOC, and the specification is that the length is 60m, the inner diameter is 0.32mm, and the film thickness is 1.8 mu m; the carrier gas is helium with the purity more than or equal to 99.999 percent; the temperature of a sample inlet is 180 ℃; adopting a constant flow mode, wherein the column flow is 2.0mL/min, and the split ratio is 10; the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 6 min; raising the temperature to 100 ℃ at the temperature rise rate of 5 ℃/min; then the temperature is raised to 230 ℃ at the temperature rise rate of 30 ℃/min and is kept for 15min.
6. The method for simulated determination of benzene series migration to cigarette smoke in cigarette filter sticks according to claim 1, characterized in that in step (2), mass spectrum conditions are as follows: the temperature of the auxiliary interface is 230 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature: 150 ℃, solvent delay time: 3.8min; a selective ion monitoring mode is employed.
7. The method for simulating and measuring the benzene series migration to the cigarette smoke in the cigarette filter stick according to claim 1, wherein in the step (2), the method for calculating the migration rate comprises the following steps: the amount of the simulated actual pumped benzene series components measured by a gas chromatography-mass spectrometer is divided by the total amount of the benzene series components to obtain the mobility;
when the measurement of actually sucked benzene series components is simulated, replacing a new filter stick after blowing every time, blowing again, and using not less than 10 filter sticks in total;
the total amount detection method of the benzene series components comprises the following steps: replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8-15min by using gas at 160-200 ℃, continuously purging the new filter stick again after purging is finished, purging not less than 10 filter sticks totally, and then measuring the total benzene series components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911109247.6A CN110850010B (en) | 2019-11-13 | 2019-11-13 | Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911109247.6A CN110850010B (en) | 2019-11-13 | 2019-11-13 | Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110850010A CN110850010A (en) | 2020-02-28 |
| CN110850010B true CN110850010B (en) | 2022-12-06 |
Family
ID=69601630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911109247.6A Active CN110850010B (en) | 2019-11-13 | 2019-11-13 | Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110850010B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102636556B (en) * | 2012-04-23 | 2014-06-11 | 上海烟草集团有限责任公司 | Ion molecule mass-spectrometric method for on-line detection of gas phase composition of cigarette smoke mouth by mouth |
| CN203772673U (en) * | 2014-03-18 | 2014-08-13 | 广东中烟工业有限责任公司 | Device for testing desorption rate of cigarette material |
| CN204287144U (en) * | 2014-12-03 | 2015-04-22 | 河南中烟工业有限责任公司 | One grows tobacco aspirator |
| CN105572306B (en) * | 2016-01-20 | 2017-12-08 | 江苏中烟工业有限责任公司 | The detection means and its method that air mass flow is distributed during a kind of cigarette smoking |
| CN108490097A (en) * | 2018-05-16 | 2018-09-04 | 云南中烟工业有限责任公司 | A kind of detection method of the volatile organic compounds burst size of nanometer of filter tip |
-
2019
- 2019-11-13 CN CN201911109247.6A patent/CN110850010B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110850010A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110850009B (en) | Simulation determination method for migration of cooling agent component in cigarette filter stick to cigarette smoke | |
| Ueta et al. | Determination of volatile organic compounds for a systematic evaluation of third-hand smoking | |
| CN104198573B (en) | A kind of cigarette mainstream flue gas on-line analysis and its special on-line analysis device | |
| CN101871922B (en) | Method for pyrolyzing tobacco additive and trapping and analyzing pyrolysis product | |
| CN110850008B (en) | Method and device for measuring migration quantity of volatile components in cigarette blasting beads | |
| CN104950065B (en) | A kind of whole smoke trapping and on-line analysis apparatus and method | |
| Cropper et al. | Development of the GC-MS organic aerosol monitor (GC-MS OAM) for in-field detection of particulate organic compounds | |
| CN102680603A (en) | Method for measuring contents of four tobacco-specific nitrosamines (TSNAs) in cigarette main stream smoke | |
| Agrios et al. | Online coupling of pure O2 thermo-optical methods–14C AMS for source apportionment of carbonaceous aerosols | |
| CN110850010B (en) | Simulation determination method for migration of benzene series substances in filter stick to cigarette smoke | |
| CN109799302B (en) | Near-online detection method for medium-volatility organic compounds | |
| CN205483696U (en) | Tobacco heating is volatility aroma components entrapment device and detecting system down | |
| CN211553882U (en) | Filter rod additive heat migration volume measuring device | |
| CN203758976U (en) | Device for measuring release amount of HCN generated during oxygen-deficient combustion of tobaccos | |
| CN108693264A (en) | The detection device and detection method of a kind of bouquet components the amount of migration for special flavoring filter stick | |
| CN103884794A (en) | Method for measuring trace hydrogen sulfide gas in atmosphere | |
| CN108490097A (en) | A kind of detection method of the volatile organic compounds burst size of nanometer of filter tip | |
| CN110850007B (en) | Method for measuring phthalate component migration in filter stick by simulating real smoking of cigarette | |
| CN112763633A (en) | Device and method for determining heated migration components of filter stick additive by dynamic headspace method | |
| CN110879265B (en) | Method for simulating and measuring heat migration quantity of formaldehyde and acetaldehyde to smoke in cigarette blasting beads | |
| CN110988204B (en) | Method for measuring migration volume of colorant smoke in filter tip by simulating cigarette smoking | |
| CN214252162U (en) | Purging pipe for measuring heated migration components of cigarette filter stick by dynamic headspace method | |
| CN214174260U (en) | Device for measuring heated migration components of filter stick additive by dynamic headspace method | |
| CN112120277A (en) | Purging pipe and purging method for purging and detecting cigarette filter stick | |
| CN210166343U (en) | On-line measuring device for cigarette smoldering side-stream smoke gas-phase component photoionization efficiency curve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |