CN110967427B - Method for high-stability determination of ammonia content in cigarette mainstream smoke by adopting ion chromatography - Google Patents

Abstract

A method for determining ammonia content in mainstream cigarette smoke by ion chromatography with high stability disclosed by the invention comprises the following steps: S1. capturing the total particulate matter and gaseous ammonia in mainstream cigarette smoke; S2. using cut tobacco raw materials The prepared extractant extracts the total particulate matter to obtain an extract, and dilute hydrochloric acid captures gaseous ammonia to obtain a trap, which is mixed with equal volumes of the extract and the trap to be diluted to a constant volume and filtered; S3. The filtrate is analyzed by ion chromatography to obtain the cigarette sample Ion chromatogram, qualitatively based on retention time, quantified by external standard method, deducted the ammonia content in the extractant to obtain the ammonia content in mainstream cigarette smoke, using the extractant prepared from cut tobacco raw materials to improve the stability of ammonia detection results.

Description

A high-stability method for the determination of ammonia content in mainstream cigarette smoke by ion chromatography method

technical field

The invention relates to the field of flue gas analysis, in particular to a method for determining ammonia content in mainstream cigarette smoke with high stability by ion chromatography.

Background technique

Ammonia is one of the seven harmful components in mainstream cigarette smoke, and the amount of ammonia released directly affects the hazard index of the product. At present, there are relatively many studies on the amount of ammonia released in mainstream smoke of conventional cigarettes. The tobacco industry has established the industry standard method YC/T377-2010 for the analysis of ammonia content in mainstream flue gas by ion exchange chromatography. rising continuously, which is not conducive to the determination of accurate ammonia value. Later, the standard pretreatment method was revised to stabilize the stability of the liquid to be tested by injecting samples under low temperature conditions. However, this method has higher requirements on the sampler and cannot control the release of ammonia during the extraction process. The precursors release ammonia.

SUMMARY OF THE INVENTION

In order to solve the above problems, the present invention provides a high-stability method for determining ammonia content in mainstream cigarette smoke by ion chromatography, using an extractant prepared from cut tobacco raw materials, improving the stability of ammonia detection results and having high detection sensitivity.

The technical solution solved by the present invention is to provide a method for measuring ammonia content in mainstream cigarette smoke with high stability by using ion chromatography, comprising the following steps:

S1. Capture total particulate matter and gaseous ammonia in mainstream cigarette smoke;

S2. Extract the total particulate matter with the extraction agent prepared from the cut tobacco raw material to obtain an extract, capture gaseous ammonia with dilute hydrochloric acid to obtain a trap, and filter the equal volume of the mixed extract and the trap solution after diluting to a constant volume;

S3. The filtrate is analyzed by ion chromatography to obtain the ion chromatogram in the cigarette sample, qualitatively based on the retention time, quantified by the external standard method, and the ammonia content in the extractant is deducted to obtain the ammonia content in the mainstream cigarette smoke.

Preferably, the preparation steps of the extractant prepared from the cut tobacco raw material are as follows: heating the cut tobacco sprayed with glycerin at 300-400°C, and dilute hydrochloric acid to capture the flue gas and dilute to constant volume to obtain the extractant prepared from the cut tobacco raw material.

Preferably, the chromatographic column for the ion chromatographic analysis is CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30°C, and the conductivity cell temperature is is 35°C and the suppressor current is 132mA.

Preferably, the S2 extraction time is 15-20min, and the extraction method is ultrasonic vibration extraction.

Preferably, the S1 total particulate matter is captured by Cambridge filter discs, and the gaseous ammonia is captured by 10 mmol/L dilute hydrochloric acid.

Preferably, before the S1, the step further includes: balancing the cigarette, the equilibrium condition temperature is (22±1)° C., the relative humidity is (60±3)%, and the equilibration time is 48h.

Preferably, the amount of the glycerin is 10-20% of the mass of the cut tobacco.

Preferably, the dilute hydrochloric acid concentration is 10 mmol/L.

In this scheme, the atomizing agent glycerol is used to atomize the cut tobacco to release the smoke, and after being absorbed by dilute hydrochloric acid, an extractant containing the cut tobacco raw material is obtained. There are 34 kinds of organic compounds, mainly esters, aldehydes and ketones, etc. Since glycerin can extract ketones in cut tobacco, the carbonyl of ketones on the one hand inhibits the precursor of ammonia in cigarette smoke, which is unstable. Substances such as urotropine are reversibly degraded into aldehydes and ketones and ammonia. On the other hand, the carbonyl group of ketones will undergo Maillard reaction with the stable amino group in the flue gas, which plays the role of anchoring ammonia, so the measured results are more stable. .

The beneficial effects of the present invention are as follows:

1. Extraction with an extractant prepared from cut tobacco raw materials, using ketones in cut tobacco to inhibit the degradation of unstable ammonia precursors such as urotropine, or anchoring ammonia in cigarette smoke to improve ammonia detection The stability of the liquid, the repeatability of the test results are good, and the universality is high;

2. Use ion chromatography to accurately and quickly determine the ammonia content in the sample solution, which is suitable for analyzing the ammonia release of cigarette samples in large quantities;

3. The CS16 chromatographic column is used to determine the ammonia content in mainstream cigarette smoke, with high detection sensitivity and wide linear range.

Description of drawings

Fig. 1 is embodiment 1 ion chromatography analysis collection of illustrative plates;

Fig. 2 is embodiment 2 ion chromatography analysis collection of illustrative plates;

Fig. 3 is the ion chromatography analysis spectrum of Example 3.

Detailed ways

In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below with reference to specific embodiments, but the present invention is not limited thereto.

Example 1

Preparation of extractant containing cut tobacco raw material: after spraying 15% glycerin in 10g cut tobacco, heating cut tobacco at 300°C and collecting flue gas with 100ml concentration of 10 mmol/L dilute hydrochloric acid solution, the gained absorbing liquid uses 40 ml 10mmol/L dilute hydrochloric acid Capture the flue gas and dilute it to 200ml as an extractant for later use.

Draw the standard curve: take the ammonia standard solution of 1000 μg/ml as the mother liquor, dilute the mother liquor with 10 mmol/L dilute hydrochloric acid, and the dilution ratios are 2000 times, 1000 times, 500 times, 250 times and 125 times in turn. CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30 °C, the conductivity cell temperature is 35 °C, and the suppressor current is 132 mA ions The peak area of the chromatogram was determined by chromatographic analysis, and the standard curve was drawn by linear regression. The equation of the standard curve was: Y=0.209X

Sample determination: The commercial cigarette sample A was equilibrated at (22±1) ℃ and relative humidity (60±3)% for 48 hours, and then the length of the butt of the smoking cigarette was determined and marked, and 4 cigarettes were smoked.

The total particulate matter in mainstream flue gas was captured by a Cambridge filter, and gaseous ammonia was collected with 20 mL of dilute hydrochloric acid with a concentration of 10 mmol/L to obtain a capture solution;

Put the Cambridge filter that captures the mainstream smoke of 4 cigarettes into a 50mL conical flask, add 20mL of extractant prepared from cut tobacco raw materials, and then place the conical flask on a speed-regulating shaker for 15 min. The frequency of the device was set to 160 r/min to obtain the extract. 5mL of the above-mentioned granular phase extract and 5mL of the gas phase trapping solution were respectively accurately pipetted into a 25mL volumetric flask and the volume was constant. After shaking, use a 0.45μm aqueous syringe filter. filter to be tested;

Use the same ion chromatographic conditions as in the preparation of the standard curve, the chromatographic column is CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30 °C, and the conductivity The cell temperature was 35°C, and the suppressor current was 132 mA. The peak time was 7.407 min and the peak area was determined by ion chromatography. 1/5 is used as blank, and the ammonia content in mainstream cigarette smoke is obtained after deduction.

The results of measuring the content of ammonia in the ammonia solution to be tested at different times are shown in Table 1. It can be seen from the table that the ammonia content measured by the method of the present invention is relatively stable and does not change significantly, and the former standard method YC/T377- The ammonia content measured in 2010 varied widely.

Table 1Example 1 Test smoke samples using new method and standard method YC/T377-2010 Ammonia content stability analysis results① (unit: μg/cig)

Note ① "I" means the change of ammonia content measured by the method of this patent; "II" means the change of ammonia content measured by the standard method YC/T377-2010.

According to this method, the amount of ammonia released in the mainstream smoke of cigarette A was analyzed, and the measurement was repeated 5 times, as shown in Table 2. The results showed that the repeatability of this experimental method was good.

Table 2 Repeatability results of the experimental method (unit: μg/cig)

Example 2

Preparation of extractant containing cut tobacco raw material: after spraying 20% glycerin in 5g cut tobacco, heating cut tobacco at 400°C and collecting flue gas with 100ml concentration of 10 mmol/L dilute hydrochloric acid solution, the gained absorption liquid is 40 ml 10 mmol/L dilute hydrochloric acid Capture the flue gas and dilute it to 200ml as an extractant for later use. Draw the standard curve: take the ammonia standard solution of 1000 μg/ml as the mother liquor, dilute the mother liquor with 10 mmol/L dilute hydrochloric acid, and the dilution ratios are 2000 times, 1000 times, 500 times, 250 times and 125 times in turn. CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30 °C, the conductivity cell temperature is 35 °C, and the suppressor current is 132 mA ions The peak area of the chromatogram was determined by chromatographic analysis, and the standard curve was drawn by linear regression. The equation of the standard curve was: Y=0.218X

Sample determination: The commercial cigarette sample C was equilibrated under the conditions of (22±1) ℃ and relative humidity (60±3)% for 48 hours, then the length of the butt of the smoking cigarette was determined and marked, and 4 cigarettes were smoked.

The total particulate matter in mainstream flue gas was captured by a Cambridge filter, and gaseous ammonia was collected with 20 mL of dilute hydrochloric acid with a concentration of 10 mmol/L to obtain a capture solution;

Put the Cambridge filter that captured the mainstream smoke of 4 cigarettes into a 50mL conical flask, add 20mL of extractant prepared from cut tobacco raw materials, and then place the conical flask on a speed-regulating shaker to shake for 20 min. The frequency of the device was set to 160 r/min to obtain the extract, and 5 mL of the above-mentioned granular phase extract and 5 mL of the gas phase trapping solution were accurately pipetted into a 25 mL volumetric flask to dilute to volume. Measurement;

Use the same ion chromatographic conditions as in the preparation of the standard curve, the chromatographic column is CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30 °C, and the conductivity The temperature of the cell is 35°C, and the current of the suppressor is 132 mA. The peak time is 7.413min and the peak area is determined by ion chromatography, as shown in Figure 2. According to the standard curve, the ammonia content is measured, and the ammonia content in the extraction agent 1/5 is used as blank, and the ammonia content in mainstream cigarette smoke is obtained after deduction.

Analyze the ammonia content in the liquid to be tested at regular intervals, and check whether the ammonia release amount is stable.

It can be seen from Table 3 that the thin cigarette C can stabilize the ammonia content of the liquid to be tested within a certain time range, so this method has good universality.

Table 3 Stability analysis results of C ammonia release from thin cigarettes (unit: μg/cig)

Example 3

Preparation of extractant containing cut tobacco raw materials: after spraying 10% glycerin in 8g cut tobacco, heating cut tobacco at 350°C and collecting flue gas with 100ml of diluted hydrochloric acid solution with a concentration of 10 mmol/L, the obtained absorption liquid is diluted with 10 mmol/L diluted hydrochloric acid To 500ml as the extraction agent prepared from cut tobacco raw materials for standby use.

Draw a standard curve: take 1000 μg/ml ammonia standard solution as the mother solution, dilute the mother solution with the dilute hydrochloric acid, and the dilution ratios are 2000 times, 1000 times, 500 times, 250 times, and 125 times in turn. The chromatographic column used is CS16, The mobile phase was 0.045 mol/L methanesulfonic acid solution, the flow rate was 1.0 mL/min, the injection volume was 25 μL, the column temperature was 30 °C, the conductivity cell temperature was 35 °C, and the suppressor current was 132 mA. The peak area of the chromatogram was determined by the method, as shown in Figure 3, and the standard curve was drawn by linear regression. The equation of the standard curve is: Y=0.196X

Sample determination: The commercial cigarette sample A was equilibrated at (22±1) ℃ and relative humidity (60±3)% for 48 hours, and then the length of the butt of the smoking cigarette was determined and marked, and 4 cigarettes were smoked.

The total particulate matter in mainstream flue gas was captured by a Cambridge filter, and gaseous ammonia was collected with 20 mL of dilute hydrochloric acid with a concentration of 10 mmol/L to obtain a capture solution;

Put the Cambridge filter that captured the mainstream smoke of 4 cigarettes into a 50mL conical flask, add 20mL of extractant prepared from cut tobacco raw materials, and then ultrasonically extract the conical flask for 15 min, and the ultrasonic frequency is 3000HZ to obtain the extraction. liquid, respectively accurately pipette 5mL of the above-mentioned granular phase extract and 5mL of the gas phase trapping solution to a 25mL volumetric flask to constant volume, shake well and filter with a 0.45μm aqueous syringe filter to be tested;

Use the same ion chromatographic conditions as in the preparation of the standard curve, the chromatographic column is CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the injection volume is 25 μL, the column temperature is 30 °C, and the conductivity The temperature of the cell is 35℃, and the current of the suppressor is 132 mA. The peak time is 7.403min and the peak area is determined by ion chromatographic analysis, and the volume is determined. According to the standard curve, the ammonia content is measured, which is 1/5 of the ammonia content in the extractant. As a blank, the ammonia content in mainstream cigarette smoke was obtained after deduction.

Analyze the ammonia content in the liquid to be tested at regular intervals, and investigate whether the ammonia release amount is stable, and compared with the results obtained in Example 1, it can be known from Table 4 that this method measures the ammonia content with high consistency and stable results.

Table 4 Ammonia stability results

The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (5)

1. A method for measuring the ammonia content in the mainstream smoke of cigarettes with high stability by adopting ion chromatography is characterized by comprising the following steps:

s1, collecting total particulate matters and gaseous ammonia of main stream smoke of cigarettes;

s2, extracting the total particulate matter by using an extractant prepared from tobacco shred raw materials to obtain an extraction liquid, collecting gaseous ammonia by using dilute hydrochloric acid to obtain a collection liquid, diluting the mixed extraction liquid and the collection liquid with equal volumes to a constant volume, and filtering;

s3, obtaining an ion chromatogram map in the cigarette sample by analyzing the filtrate through ion chromatography, quantifying by using an external standard method according to the qualitative retention time, and deducting the ammonia content in the extracting agent to obtain the ammonia content in the mainstream smoke of the cigarette; the preparation steps of the extractant prepared from the cut tobacco raw material are as follows: heating the tobacco shreds sprayed with the glycerol at 300 ℃, and collecting the smoke with dilute hydrochloric acid, diluting and fixing the volume to obtain an extracting agent prepared from the tobacco shreds; the using amount of the glycerol is 15% of the mass of the cut tobacco; the chromatographic column of the ion chromatographic analysis is CS16, the mobile phase is 0.045 mol/L methanesulfonic acid solution, the flow rate is 1.0 mL/min, the sample volume is 25 muL, the column temperature is 30 ℃, the conductivity cell temperature is 35 ℃, and the suppressor current is 132 mA.

2. The method for high-stability determination of ammonia content in cigarette mainstream smoke by ion chromatography according to claim 1, wherein the S2 extraction time is 15-20min, and the extraction mode is ultrasonic oscillation extraction.

3. The method for high-stability determination of the ammonia content in the mainstream smoke of cigarettes by using the ion chromatography as claimed in claim 1, wherein the S1 total particulate matters are captured by Cambridge filter discs, and the gaseous ammonia is captured by 10mmol/L diluted hydrochloric acid.

4. The method for highly stably measuring the ammonia content in the mainstream smoke of a cigarette by using ion chromatography according to claim 1, wherein the step of S1 is preceded by the steps of: balancing the cigarettes at the temperature of 22 +/-1 ℃ and the relative humidity of 60 +/-3% for 48 h.

5. The method for high-stability determination of ammonia content in cigarette mainstream smoke by ion chromatography according to claim 1, wherein the concentration of the dilute hydrochloric acid is 10 mmol/L.

Images