CN108181405A - The method that gas chromatography measures moisture content in cigarette filter rod - Google Patents
The method that gas chromatography measures moisture content in cigarette filter rod Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention belongs to the physical and chemical inspection technical field of cigarette filter rod, the method for moisture content in especially a kind of gas chromatography measure cigarette filter rod.A kind of method that gas chromatography measures moisture moisture content in cigarette filter rod, according to cigarette filter rod physicochemical property, the running parameter of selection and gas chromatograph to sample pre-treatments, internal standard compound has carried out selection optimization, with accuracy height, precision and reproducible, the advantages that detection limit is low, and the range of linearity is wide, and analysis time is short.This method is realizes that quick and precisely measuring moisture in cigarette filter rod provides possibility, improve checkability and the speed of response, ensure that Products quality safety is carefully controlled, it is provided a strong guarantee for enterprise's smoking material technical standard that becomes better and approaching perfection day by day, the development for low tar Less harmful cigarette is provided with reference to thinking and technical support.
Description
Technical field
The invention belongs to the physical and chemical inspection technical field of cigarette filter rod, especially a kind of gas chromatography measures cigarette filter rod
The method of middle moisture content.
Background technology
Filter tip is cigarette important component, has larger impact to the transmission capacity and aesthetic quality of cigarette smoke.Moisture (contains
Water rate) be filter stick physical property an important indicator, GB/T 5605-2011《Cellulose acetate filter rod》With GB/T 15270-
2001《Tobacco and tobacco product polypropylene fiber tow filter rods》Limitation requirement to filter stick moisture is≤8% and≤2% respectively, this is
Because filter stick moisture content is excessively high, easily goes mouldy, and may influence to take hot melt adhesive performance at mouth, cause during storage
Seam broken and other issues.Filter tip moisture content can directly affect moisture content of flue gas adopting, and flue gas moisture then has cigarette sense organ comfort level
Great influence, flue gas moisture is suitable for the soft exquisiteness of then flue gas, irritation is small, sensory comfort is preferable；When moisture content of flue gas adopting is low,
It can lead to that flue gas drying, irritation become larger, sensory comfort reduces.Therefore, the accurate of filter tip moisture content is measured also with important
Meaning.
GB/T 22838.8-2009《The 8th part of measure of cigarette and filter stick physical property：Moisture content》Define cigarette filter
The baking oven assay method of stick moisture, this method is by detecting weightlessness hundred of 10 filter sticks in (100 ± 2) DEG C baking oven after dry 2h
Ratio is divided to determine filter stick moisture content.This method principle is simple and convenient to operate；But find that this method may in actual application
There are problems that.Since filter stick is by Diacetate cellulose tow (small part product uses polypropylene tows), glue, cellulose paper
(only furrowfilter rod) and forming paper form；Hot environment can cause some low-boiling point materials or thermal decomposition product to discharge.As filter stick,
Glue used in cellulose paper and forming paper and Diacetate cellulose tow may decompose release acetic acid at high temperature；For silk
The glyceryl triacetate of beam-curable may directly discharge under the high temperature conditions；These factors can lead to the filter of oven method measuring
Stick moisture content is higher than actual value, so as to react the real quality of filter stick level or even cause identifier in work is examined
Member's erroneous judgement.
Karl_Fischer method is classical water and basis weight method, can the true moisture of Accurate Determining sample, but by
It in the multiple element compound that filter stick is made of tow, glue and paper, can not be completely dissolved in organic solvent, cause to use and be somebody's turn to do
It is interfered during method more；In addition, this method batch test efficiency is not high；Contain it is therefore contemplated that measuring filter stick with Karl_Fischer method
Water rate is not optimal selection.With the increasingly strict of requirement is analyzed, chromatographic technique is more ripe, and capillary chromatographic column is due to it
The characteristics of high resolution, quantitative result are accurate, stability is good is analyzed more suitable for batch sample.Applied to organic solvent, coating
Etc. the measure of moisture in matrix.
Therefore, it is necessary to further research and develop filter stick moisture content detecting method based on gas chromatography, ensure inspection
The accuracy of measured data provides technical support for filter rod quality control and industry correlative study.
Chinese invention patent (the application number of applicant's application：CN201510967111.4 gas chromatography measure) is disclosed
The method of cigarette filter rod moisture, this method according to cigarette filter rod physicochemical property, selection to sample pre-treatments, internal standard compound and
The running parameter of gas chromatograph has carried out selection optimization, has that accuracy is high, precision and reproducible, and detection limit is low, line
The advantages that property range is wide, and analysis time is short.The patent is the pre-stage test analysis method of applicant, is sent out during practice
Existing, there is the result of detection the condition of internal standard compound, chromatographic column and gaschromatographic mass spectrometry in cigarette filter rod determination of moisture
Very big influence.In order to seek unity of standard, realize that accuracy is high, precision and reproducible, detection limit is low, can realize water in filter stick
Divide the rapid and accurate determination of content, need further to optimize condition.
Goal of the invention
In order to solve the technical issues of above-mentioned, the present invention provides a kind of gas chromatographies to measure moisture content in cigarette filter rod
Method, the advantage is that accuracy height, precision and reproducible, detection limit is low, can realize the fast of moisture in filter stick
Fast Accurate Determining.
In order to realize above-mentioned purpose, present invention employs following technical solutions：
The method that gas chromatography measures moisture content in cigarette filter rod, this method include the following steps：
(1) extractant
A certain amount of acetonitrile is pipetted, with isopropanol, obtains the interior extraction solution for being designated as ethane nitrile content as 3mL/L, this
Solution should be now with the current；
(2) standard solution
A certain amount of standard substance is weighed in extractant, is accurate to 0.01mg, at least six standard solution is prepared, obtains
Biodiversity concentration is respectively 0,0.5,1.5,2.5,3.5, the series standard working solution of 5.0mg/mL, this solution should show with existing
With.
(3) instrument and equipment
Assay balance：Sensibility reciprocal is 0.1mg；
Gas chromatograph：Equipped with thermal conductivity cell detector, recorder and integrator or other suitable data processing equipments；
Capillary chromatographic column：Internal diameter 0.53mm, 40.0 μm of film thickness, column length 30m.Stationary phase is bonding polystyrene-diethyl
Alkenyl benzene；
Gas chromatograph operating condition is as follows：
- carrier gas：Helium, constant current mode, flow 7mL/min；
- injector temperature：260℃；
- sampling volume：2μL；Split sampling, split ratio：5:1；
- column oven temperature program：170 DEG C of initial temperature keeps 4min；260 DEG C are risen to 90 DEG C/min rates, is kept
30min；
- detector temperature：260℃；Reference flow 20mL/min；Make-up gas flow 2mL/min；
(4) sample pre-treatments
Laboratory sample or sets itself sampling side are extracted according to the sampling prescription that GB/T 5605 is provided according to experiment purpose
Method extracts laboratory sample；Rear chamber is gentle puts for sample sealing, and detection was completed in 9 days；
5 filter sticks are randomly selected, weighs, is accurate to 0.1mg；Filter stick is longitudinally torn, then laterally to be cut into 1~2cm long small
Section, is placed in 250mL conical flasks, adds in 100mL extractants, with 150r/min oscillation extraction 30min after sealing, takes supernatant liquor
Cross the laggard gas chromatograph detection of 0.45 μm of organic phase filter membrane；The sample solution should complete machine analysis in 48h；
Tear initiation filter stick is answered to take out quick-fried pearl when cutting containing quick-fried pearl filter stick, then segment is put into conical flask and weighs；
(5) standard curve making
2 μ L standard solution is taken to inject gas chromatograph respectively, record the peak height or peak area of moisture and internal standard compound, at least into
Row measures twice；
Calculate the ratio of peak or peak area ratio of each standard solution moisture and internal standard compound, make moisture concentration and ratio of peak or
The relation curve of peak area ratio calculates regression equation, and regression curve related coefficient should be greater than 0.999；
The making of a standard curve is carried out per inspection lot；In addition, every 20 samples should be injected after measuring one it is medium dense
Standard solution is spent, if acquired results differ 5% with initial value, then should re-start the making of entire standard curve；
(6) blank test
Due to solvent absorption moisture, determination sample blank moisture moisture content is answered；Sample blank should use identical with sample
Method is extracted, is analyzed；
(7) it measures
Sample extraction liquid and blank extract liquor are injected into gas chromatograph respectively, calculate peak area ratio or ratio of peak；
Replication twice, calculates the average value of parallel determination at identical conditions；
(8) result is calculated and is stated
Under gas phase condition identical with making working curve, filter stick extract liquor calculates moisture after gas chromatographic analysis
Compare with the peak height (or peak area) of internal standard compound, moisture concentration in extraction solution is obtained by regression equation calculation, filter stick sample is aqueous
Rate is calculated by following formula：
In formula：
W --- filter stick moisture content, unit %；
C1--- moisture concentration in extraction solution, unit are every milliliter of milligram；
C0--- moisture concentration in blank solution, unit are every milliliter of milligram；
V --- extraction liquor capacity, unit is milliliter；
M --- filter stick weight, unit are gram；
Take twice parallel determinations average value as final testing result, be accurate to 0.01%；
Parallel determinations relative deviation should be less than 5% twice.
The method that a kind of gas chromatography of the present invention measures moisture moisture content in cigarette filter rod, according to cigarette filter rod physics and chemistry
Characteristic, the running parameter of selection and gas chromatograph to sample pre-treatments, internal standard compound have carried out selection optimization, have had accuracy
The advantages that height, precision and reproducible, detection limit is low, and the range of linearity is wide, and analysis time is short.This method is realizes quick and precisely
It measures moisture in cigarette filter rod and provides possibility, improve checkability and the speed of response, it is ensured that Products quality safety
It is carefully controlled, it is provided a strong guarantee for enterprise's smoking material technical standard that becomes better and approaching perfection day by day, is the development of low tar Less harmful cigarette
Exploitation is provided with reference to thinking and technical support.
Description of the drawings
Fig. 1 is alcohols and glyceryl triacetate reaction equation.
Fig. 2 is typical sample gas chromatogram (0.864min- air peaks；0.997min- water；1.670min- acetonitrile；
1.880min- isopropanol；33.059min- glyceryl triacetate).
Fig. 3 is the moisture and internal standard response diagram obtained using this method.
Fig. 4 is the moisture standard curve obtained using this method.
Influence of Fig. 5 conditions of storage to experiment.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
1. reagent
1.1 water, tertiary effluent
1.2 acetonitriles (99.9%),
1.3 isopropanols (99.8%),
1.4 extractant
12mL acetonitriles are pipetted, with isopropanol to 4000mL, obtain the extraction solution that ethane nitrile content is 3mL/L, this is molten
Liquid should be now with the current.
1.5.1 solvent blank solution：Tertiary effluent
1.5.2 moisture standards solution
Weigh 0 respectively, 0.05,0.15,0.25,0.35,0.50g water (being accurate to 0.1mg) in 6 100mL volumetric flasks,
With extraction solution constant volume, obtain biodiversity concentration be respectively 0,0.5,1.5,2.5,3.5, the series standard work of 5.0mg/mL
Solution, this solution should be now with the current.
1.6 high-purity heliums (purity is more than 99.999%)
2 instrument and equipments
2.1 conical flask with cover, 250mL
2.2 volumetric flasks, 100mL
2.3 assay balances, sensibility reciprocal 0.1mg
2.4 vortex oscillation instrument
2.5 are furnished with the gas chromatograph (Agilent Technologies, 7890A models) of thermal conductivity cell detector
3 analytical procedures
(1) solvent selects
When gas chromatography measures moisture in solid and fluid sample, generally using acetone, methanol, ethyl alcohol, isopropanol and
Sample introduction after the organic solvents such as N,N-dimethylformamide (DMF) are extracted or diluted to sample.
The study found that acetone and DMF can cause filter stick fibre bundle to dissolve, extraction solution becomes cloudy, even if high speed centrifugation
It is still not easy to be filtered afterwards；Sample bottle yet more difficult cleaning after extracting simultaneously, does not meet solvent selection principle, therefore does not consider acetone
With extractants of the DMF as this method.
Methanol and isopropanol are common extractants in tobacco, flue gas moisture Gas Chromatographic Method, GB/T
Then 23203.1-2013 takes machine point on extract liquor using moisture of the isopropanol as extractant extraction Cigarette grain phase
Analysis；YC/T 345-2010 use methanol as the moisture in extractant extracted tobacco and tobacco product, then will be on extract liquor
Machine is analyzed.But document shows that with glyceryl triacetate ester exchange reaction (see Fig. 1), and filter stick can occur for the alcohols solvents such as methanol
In containing a small amount of glyceryl triacetate, therefore, influence of the reaction to measurement result has been investigated in experiment.Although the study found that filter
The a small amount of glyceryl triacetate contained in stick under certain condition may be with these alcohols materials (under high temperature, such as injection port)
Ester exchange reaction occurs, but chemically from the point of view of reaction equation, alcohols and glyceryl triacetate reaction can't generate water (see Fig. 1)；
It more also research shows that the carbochain of alcohol is longer, is more difficult to carry out ester exchange reaction, along with the steric hindrance of isopropanol in itself is imitated
Should, isopropanol generation ester exchange reaction more difficult than methanol.Therefore, comprehensive various aspects factor, it is finally determining to be using isopropanol
This method extractant.Later experiments result also turns out that for this method using isopropanol as extractant, sample solution measurement result is steady
It is fixed, harmful effect is not caused to detection data.
(2) internal standard selects
Inner mark method ration can eliminate the influence to measurement result such as instrument, operation relative to external standard method, improve and measure precision
Degree, so Water By Gas Chromatography timesharing uses inner mark method ration mostly.Tobacco business Water By Gas Chromatography timesharing is normal
Mainly there are methanol or ethyl alcohol, isopropanol and acetone etc. with internal standard.But there is literature research to show that alcohols under certain condition can be with three
Ester exchange reaction occurs for acetin.Result, it is believed that avoid potentially reacting possibility, methanol, ethyl alcohol should not be used to make
For this experiment interior label.
And there are a small amount of residual acetone in filter stick, therefore can not also use internal standard of the acetone as this method.
According to internal standard alternative condition：Stablize, purity height；It should not contain internal standard substance in sample itself；The position at internal standard peak
It is between each component to be measured or relatively near therewith；It can dissolve each other with sample and not chemically react.Acetonitrile has been investigated as internal standard
Feasibility.Acetonitrile also known as methyl cyanide, can be with water or alcohol infinitely dissolve.It is straight to have more analysis worker at present according to the literature
It connects and uses acetonitrile solution sample introduction gas-chromatography, illustrate that acetonitrile can use, and will not as a kind of solvent of gas chromatographic sample introduction
Damage gas chromatographic column.The experimental results showed that under selected chromatographic condition, the chromatographic peak separation of water, acetonitrile and solvent isopropanol
Degree is high, and the peak shape of water and internal standard acetonitrile is good.Therefore, internal standard of the acetonitrile as this method is selected.
(3) chromatographic column selects
It is found by Literature Consult, when early stage gas chromatography detects moisture, mostly using filling post separation analysis, filler
Generally porous polymer bead, Porapak Q (ethylvinylbenzene and the copolymerized porous bead of divinylbenzene) and
Chromosorb 102 etc..With chromatographic technique maturation, there is resolution ratio, detection time, quantitative result, stability etc.
More outstanding capillary chromatographic column.Capillary column is generally divided into three types：Wall applies open tubular column (WCOT), the coated open pipe of carrier
Column (SCOT) and Porous _ layer open tubular column (PLOT).Many standards start using capillary chromatographic column for water analysis, such as GB/
T 23203.1-2013 use PoraPLOT Q capillary chromatographic columns (30m × 0.53mm × 40.0 μm)；YC/T 345-2010 are adopted
With PoraPLOT U-capillaries column (25m × 0.53mm × 20.0 μm), PoraPLOT Q capillary columns (25m × 0.53mm ×
20.0μm)；Thermo Fisher Scientific companies recommend TG-BOND Q capillary columns (30m × 0.32mm × 10
μm)。
Compare industry in common Porapak Q (190 DEG C), (250 DEG C) packed columns of Chromosorb 102 and
The capillary columns performances such as PoraPLOTU (190 DEG C), PoraPLOT Q (290 DEG C), TG-BOND Q (300 DEG C), it is found that
Porapak Q, Chromosorb 102 packed column and PoraPLOT U-capillary column highest heatproofs are relatively low, and three second in extract liquor
Acid glyceride boiling point is in 260 DEG C or so (can accumulate in the chromatography column, pollute chromatographic column), therefore Porapak Q, Chromosorb
102 packed columns, PoraPLOT U-capillary columns are not suitable for this method；Testing middle discovery, TG-BOND Q capillary columns
It is not so good as PoraPLOT Q chromatographic columns (being shown in Table 1) on separating effect.From Figure 2 it can be seen that using column length 30m, internal diameter 0.53mm, film thickness
40.0 μm of PoraPLOT Q columns, water, acetonitrile and isopropanol chromatographic isolation are good, and peak shape is suitable, therefore, it is recommended that the capillary column
Preferred chromatographic column for filter stick measurement of water-content coefficient.
The separating degree of 1 two kinds of pillars of table
Note is 1.：R >=1.5 are kept completely separate, and R is bigger, and component separation is better.
(4) type carrier gases and flow
Type carrier gases are affected to the sensitivity of TCD detectors.In principle, the difference of carrier gas and determinand heat transfer coefficient is got over
It is big better, therefore sensitivity is high when making carrier gas than nitrogen when hydrogen or helium make carrier gas.And from safety considerations, hydrogen conduct
Carrier gas can bring inconvenience to experiment, therefore select by the use of helium as this method carrier gas.
The gas chromatographic column of different inner diameters requires have different carrier gas flux ranges, the carrier gas flux one of capillary chromatographic column
As for 1~10mL/min, investigated influence of the carrier gas flux to experiment；In the case of keeping other conditions constant, by carrier gas stream
Amount is set to 1,2,3,4,5,6,7,8,9,10mL/min, experimental data is shown in Table 2.
Influence of 2 carrier gas flux of table to experiment
As seen from Table 2：As carrier gas flux increases, the peak height of moisture and acetonitrile is in the trend for first rising and stablizing afterwards, when
Peak height highest when flow is 7mL/min.The reason is that with the increase of carrier gas flux, the natural diffuseness degree of gas declines, so as to
Increase peak height；But when flow continues increase, gas molecule does not have enough times of contact just to chromatography with chromatographic column fixed phase
Column outlet end is flowed out, and counteracts the effect of natural diffuseness degree decline.
The different carrier gas flux separating effects of table 3 compare
Meanwhile as shown in Table 3, under 7mL/min carrier gas fluxes, the chromatographic peaks separating effect such as moisture, internal standard is preferable, because
Carrier gas flux is set to 7mL/min by this.
(5) injector temperature
Injector temperature is chromatographic run important parameter, and value depends on volatility, boiling point and polarity of sample etc..Generally
The temperature of maximum boiling point in a little higher than sample component is taken, to ensure the quick and complete vaporization of sample.Contain a large amount of triacetic acids in filter stick
Glyceride (258~260 DEG C of boiling point) has investigated the influence to experiment under the conditions of 220,230,240,250,260 DEG C, specific number
According to being shown in Table 4.
Influence of 4 injector temperature of table to experiment
Show：Injector temperature influences less, to ensure that glyceryl triacetate has vaporized object and interior target peak height
Entirely, it is 260 DEG C to determine injector temperature.
(6) sample size and split ratio
Sample size size changes as analysis requires, in order to ensure volume nonoverload after vaporization, shunting and not be diverted into
The sample size of sample is usually no more than 2 μ L.Split ratio size can influence shunting and discriminate against (uneven vaporization), in general, split ratio
It is bigger, it is more likely to cause shunting and discriminates against.For this purpose, the influence of 6 kinds of sample sizes and split ratio has been investigated, experimental result such as 5 institute of table
Show.
The different sample sizes of table 5, split ratio separating effect compare
Note is 2.：T ＞ 1.05 are tailing peak, and T ＜ 0.95 are leading peak.
The result shows that：Under the conditions of not shunting, moisture and impurity peaks, acetonitrile and solvent peak inferior separating effect, peak type drags
Tail is obvious；The peak type and separating effect of moisture and acetonitrile are better than under the conditions of not shunting under draining conditions.In split ratio
10:Under the conditions of 1, peak height is split ratio 5:59.2% when 1.In principle, to reduce influence of the split ratio to separation determination,
Under the premise of sample concentration and column capacity allow, small split ratio is selected；Therefore, sample size is selected as 2 μ L, split ratio 5:1.
(7) column temperature
The determining of column oven temperature is mainly determined by sample complexity and vapourizing temperature.Principle be should ensure it is to be measured
Object is kept completely separate, and ensures that all components can flow out chromatographic column, and analysis time is shorter again.The simple sample of ingredient preferably with
Constant temperature mode, to shorten analytical cycle.The sample of complicated component often needs to be detached with temperature programming；Because in constant temperature item
Under part, if column temperature is relatively low, low boiling component detaches well, and the high boiling component delivery time is too long, causes peak stretching, very
Column is caused to pollute in the chromatography column to being detained；Conversely, when column temperature is too high, low boiling component is difficult to detach again.In general, color
Compose column initial temperature most light component boiling point, final temperature should then depend on most heavy constituent boiling point close in sample.
Investigated it is constant in other conditions, starting column temperature at 140,150,160,170,180,190,200 DEG C
Chromatographic isolation situation, specific data are shown in Table 6.
6 column temperature of table influences experiment
As seen from Table 6：As temperature increases, each component retention time reduces, and especially acetonitrile retention time Forward is bright
Aobvious, the peak height of water is constant, and the peak height of acetonitrile dramatically increases.This is because column temperature increases, can be led in the case that peak area is constant
Some compound peak width is caused to narrow, peak height accordingly increases.(constant moisture peak height is because under the same conditions, peak width is constant, peak
It is high also constant therewith.)
When column temperature is higher, acetonitrile and isopropanol appearance time are closer to, and separating degree is deteriorated；When column temperature is relatively low, each group
Swarming is wide, trails than more serious (being shown in Table 7).Table 7 is it can be seen that this method is not suitable for selecting too high or too low column temperature item
Part selects 170 DEG C as starting column temperature.
The separating effect of the different column temperatures of table 7 compares
In view of, containing a small amount of glyceryl triacetate (258~260 DEG C of boiling point), especially having been investigated in extraction solution
Glyceryl triacetate appearance situation under the conditions of two kinds of 170 DEG C of constant temperature and temperature programming.Glyceryl triacetate exists at a constant temperature mode
The interior not appearances of 90min, and glyceryl triacetate appearance in 33min under temperature programming pattern, illustrate in 170 DEG C of constant temperature
Glyceryl triacetate under pattern is it is possible that be detained in the chromatography column, the constant temperature mode, which is used for a long time, to pollute chromatographic column.
Consider, it is 170 DEG C to select column temperature, and after water and acetonitrile appearance, the rapid temperature that promoted is to 260 DEG C, to drive chromatography away as early as possible
A small amount of glyceryl triacetate in column.
Simultaneously, it is contemplated that a small amount of ethyl alcohol or menthol equal solvent can be added in some special filter sticks, it may be to object
Peak and internal standard peak interfere, and influence experimental result.Ethyl alcohol and menthol standard substance are added by common filter stick respectively, investigated
The separation situation of ethyl alcohol and menthol equal solvent and component to be measured.Wherein menthol is under the present conditions without appearance, ethyl alcohol
Separating degree with acetonitrile is 1.6, and the two is kept completely separate, it is thus determined that ethyl alcohol and menthol etc. can't cause shadow to experimental result
It rings.
(8) extract liquor filtration experiment
Analysis result can be affected, investigated in view of there may be some solid impurities, careless manipulation in extract liquor
Extract liquor crosses influence whether film (0.45 μm of organic phase filter membrane), and experimental result is as shown in table 8.The result shows that cross film and only
The moisture that membrane extraction liquid detects/acetonitrile peak height response ratio does not have significant difference (p=0.46>α=0.05)；To protect pillar
And instrument, final choice film process.
Table 8 crosses film and only film influences experiment
(9) sample solution stability
In view of extractant isopropanol has certain hygroscopicity, the stability of sample solution at any time has been investigated.With same
Extractant handles 5 kinds of different types of filter sticks respectively, after each filter stick respectively takes 8 parts of sample prepare liquids to pour into chromatogram bottle sealing,
It is placed at room temperature for, carries out machine analysis at regular intervals, measurement result is shown in Table 9, table 10.
9 sample prepare liquid of table, 48 hours internal stabilities (moisture content) (%)
10 sample prepare liquid of table, 48 hours internal stabilities (relative differences with 0 hour) (%)
As can be seen that as standing time increases from table 9 and 10, sample prepare liquid moisture content change is increased slightly,
Sample solution is more stable in 48 hours, and the relative differences with the data of horse back sample introduction after the completion of processing are right within 2.5%
Measurement result has no significant effect.Therefore, sample test is completed in 48 hours after the completion of preceding processing.
(10) laboratory sample quantity
It provides to extract filter stick 750, the laboratory sample determined as sample size by GB/T 5605-2011.
Study on the stability
Two distinct types of filter stick is chosen respectively, 1,3,5 is randomly selected from sample, respectively according to this method
It is tested, respectively makees 10 parallel, result of the test such as tables 11.
Moisture content in the different Quantity of filter rod experiments of table 11
The result shows that：With the increase of Quantity of filter rod, moisture content change is little.By table 11 and Fig. 7 it is found that when filter stick is
At 5, the SD and RSD of moisture are relatively small, and therefore, it may be proper quantity to take 5 filter stick experiments.
Preci-sion and accuracy compares
By in study on the stability, it is known that the data of 5 filter sticks may be relatively stable；Therefore, it is accurate with the data of 5 filter sticks
Compare the difference (table 12) with 1,3 on the basis of degree and accuracy.
12 preci-sion and accuracy of table compares
Note is 3.：Level of significance α takes 0.05, is significant difference as p ＜ 0.05；It is pole conspicuousness as p ＜ 0.01
Difference；Otherwise it is indifference.
F inspections show：Compared with the situation of 5 filter sticks, the precision that regular plug is 1 and 3 is significantly less than 5；
The precision that ramuscule filter stick is 1 is less than 5, and the precision of 3 is identical with 5.
Double sample t inspections show：Either regular plug or ramuscule filter stick, 1,3 and the accuracy with 5 filter sticks
It is not significantly different.
Summary statistical analysis, the situation of 1 and 3 filter stick since regular plug precision is significantly less than 5, therefore
This method chooses 5 filter sticks as single experiment Quantity of filter rod.
(11) sample cutting method
In filter stick sample is weighed, such as filter stick is not torn, since surface tension of liquid acts on, filter stick can be suspended in
It extracts on solution, it is difficult to be fully wet out to influence result.Filter stick has been investigated to tear segment and do not tear segment to detection knot
Fruit influences, and the results are shown in Table 13.The result shows that two groups of data have notable difference, under the equal time, a group filter stick water content detection is torn
As a result it is apparently higher than and does not tear group.It is found to not tearing filter stick using the detection of different extraction times, it is longer not to tear sample needs
Time could extract complete (about 120min).Therefore, in sample preparation, filter stick palpus tear initiation segment again, when can save extraction
Between, improve extraction efficiency.
The different moisture content of mode (%) is cut out under the different extraction times of table 13
At present, on the market there are many special requirement filter stick, for example some contain quick-fried pearl filter stick.Because not can determine that quick-fried pearl material,
It may result in rupture in extraction process, experiment impacted, so tear initiation filter stick takes when cutting containing quick-fried pearl filter stick
Go out quick-fried pearl, then segment is put into conical flask and weighs.
(12) extract liquor volume
Extract liquor volume is selected on the basis of submerging filter stick (in 250mL conical flasks add in 5 filter sticks), investigated 100,
120th, 150mL extract liquors volume, experimental result are shown in Table 14.It can be extracted completely by table 15 visible 100,120,150mL extract liquors,
As a result indifference.Consider from solvent angle is saved, choose 100mL as this method extract liquor volume.
Influence of the 14 extract liquor volume of table to experiment
(13) mode and time are extracted
Extraction mode and extraction time are studied, ultrasound has been investigated and shaking table vibrates two kinds of extraction modes to 4 kinds
The influence of determination of moisture, the results are shown in Table 15 in specification filter stick sample.Two kinds of extraction modes are to determination of moisture result as shown in Table 20
It influences little；But there is some difference on extraction efficiency, single sample ultrasonic extraction efficiency is slightly above oscillation extraction；Work as extraction
After time is more than 30 minutes, the moisture result that two ways obtains is basically identical.In view of disposable accessible sample number
Amount, using shaking table oscillation as this method first choice.
Moisture content (%) under the conditions of the different extraction times of table 15 and extraction mode
(14) condition of storage
It is influenced to investigate environment, project team has investigated influence of the different storage conditions to filter stick moisture.Sample is by hermetic bag
It is respectively placed in after being sealed in room temperature (summer), constant temperature and humidity (22 ± 2 DEG C of temperature, relative humidity 60 ± 5%) environment, as a result
As shown in table 16.
Using the 1st day (being just derived from production line) filter stick water content detection data as standard value, with moisture relative standard deviation
(RSD) (such as Fig. 5) is mapped with the holding time, the results showed that, with the increase of holding time, filter stick moisture is presented to be increased 5 kinds of filter sticks
Big trend increases most slowly in constant-temperature constant-humidity environment, reaches within 12 days 5%, reach 10% within 27 days.Constant-temperature constant-humidity environment is stablized,
Moisture in sample will not change because of the variation of temperature, it is therefore proposed that filter stick sample is stored in constant temperature after preferably sealing
In humidity room, and detection was completed in 12 days；It if condition does not allow, then seals that rear chamber is gentle to put, and inspection was completed in 9 days
It surveys (table 17).
Influence of 16 condition of storage of table to filter stick moisture content (%)⑤
Note is 4.：A, B represents room temperature (summer), constant temperature and humidity (22 ± 2 DEG C of temperature, relative humidity 60 ± 5%) respectively.
Table 17 5% and filter stick resting period during 10%RSD (my god)
Embodiment 2
Below for measuring the homemade cigarette filter rod sample of enterprise, the detection limit, precision and recycling of this method are investigated
Rate.
Detection limit refers to the minimum flow or concentration that contained measured matter can be detected in sample, can be calculated by laxative remedy：According to
Sample moisture actual content re-scales graticule range, makes standard curve, is repeated with the minimum flow of the standard curve range of linearity
Sample introduction 10 times, calculates its standard deviation value.Using 3 times of standard deviation values of 10 sample introductions as the detection limit of method, 10 times of standards
Deviation is as quantitative limit.It obtains method detection and is limited to 0.03mg/mL, be quantitatively limited to 0.09mg/mL.
18 detection limit of table and quantitative limit
Repeated experiment is carried out using the filter stick of 5 kinds of different water cuts as analysis object respectively, in a few days and is in the daytime weighed respectively
Repetition measurement is 6 times fixed, calculates the relative standard deviation (RSD) of parallel determinations.Using the Standard Addition Method for Determination rate of recovery, to above-mentioned
5 different water cut filter sticks carry out the horizontal mark-on processing of basic, normal, high 3 kinds of various concentrations respectively；After gas phase analysis processing, calculate
Corresponding recovery of standard addition.As a result (being shown in Table 19) is shown：In a few days RSD is 1.7%~2.9%, in the daytime RSD for 2.5%~
5.6%.Recovery of standard addition is 98.1~108.4%, illustrates that this method repeatability and accuracy are preferable, can meet quantitative need
It will.
The rate of recovery and repeatability of 19 method of table
Embodiment 3
The present embodiment prepares the filter stick that a batch is not added with glyceryl triacetate, and national standard (Oven Method) and this method is respectively adopted
10 groups of control experiments are carried out, are shown in Table 20.T, which is examined, shows that Oven Method and vapor phase method testing result do not have significant difference (p=0.07
>α=0.05), show that Oven Method and vapor phase method are to the quantitative result phase of filter stick moisture when filter stick is free of glyceryl triacetate
Together.
20 two kinds of detection method control experiments of table (are free of glyceryl triacetate filter stick)
It detects the moisture content of several different size filter sticks respectively by Oven Method and vapor phase method, finds Oven Method testing result
Close to 8% limitation requirement, there are indivedual ramuscule filter stick moisture content exceeded, the results are shown in Table 21.With reference to YC/T 420-2011《Cigarette is with three
The measure gas chromatography of acetin purity》Glyceryl triacetate content in filter stick is had detected before undetermined moisture, as a result
Display after oven method measuring moisture, in filter stick glyceryl triacetate content have dropped 3.25% respectively, 3.36%, 4.31%,
5.26%th, 2.11%, 1.42%, 1.93%, 1.71%, 2.45%, 2.22%, 1.62% and 0.46%.This result shows that
When carrying out filter stick measurement of water-content coefficient using Oven Method, the glyceryl triacetate in filter stick can largely volatilize under high temperature (100 DEG C),
So as to cause severe jamming to experimental result.
The filter stick moisture content of oven method measuring is deducted to the glyceryl triacetate content loss during this, can be approximate
To theoretical moisture content (not considering a small amount of other volatile materials loss).As a result, it has been found that the filter that theoretical moisture content is measured with vapor phase method
Stick moisture content is closer to and (is shown in Table 22), shows that the reason of oven method measuring filter stick moisture content is excessively high mostlys come from three second under high temperature
The volatilization of acid glyceride.Meanwhile for the higher filter stick of glyceryl triacetate content (the ramuscule ledger line flavoring vinegar in such as this experiment
Fine filter stick), although its true moisture content is approached with other filter sticks, since filter stick glyceryl triacetate content itself is higher,
Cause volatile quantity also larger, make the higher phenomenon of moisture content result that Oven Method obtains even more serious, missed easily in real work
Sentence exceeded.
21 two kinds of detection method control experiments (filter stick containing glyceryl triacetate) of table
Note 5. GT：Glyceryl triacetate.
Embodiment 4
The verification control experiment of method has been carried out in 8 laboratories respectively.Laboratory sample selected altogether 7 kinds it is different types of
(A, B, C, D, E, F, G represent ramuscule ledger line flavoring vinegar fibre filter stick, cellulose acetate filter rod, particle-vinegar fibre to filter stick actual sample respectively
Binary compound filter candle, vinegar fibre furrowfilter rod, coaxial core filter stick, particle-vinegar fibre groove binary compound filter candle, filter stick containing capsule), often
A laboratory carries out sample pre-treatments and detection according to this method respectively, obtain the laboratory as a result, the results are shown in Table 22.By table
It can be seen that：The testing result RSD of 7 samples in 8 laboratories shows that each laboratory monitoring comparing is good within 10%.
22 filter stick water content detection result of table and statistical disposition tables of data
Using the domestic and international more common 10 kinds of filter stick moisture content of this method analysis detection, 23 are the results are shown in Table.It can by table 23
Know, cellulose acetate filter rod moisture content is between 3.65%~5.40%, less than 8% limitation requirement；Propene fibre filter stick moisture content is
1.88%, less than 2% limitation requirement.Vinegar fibre binary compound filter candle moisture content highest of the two of which containing particle, reaches 5.40%
With 4.71%, this may be to further increase its specific surface area due to containing particle binary filter stick, and water adsorption ability is obtained
Strengthen.
The moisture content (%) of several common filter sticks of table 23
Note：Capsule takes out.
Claims (1)
1. the method that gas chromatography measures moisture content in cigarette filter rod, which is characterized in that this method includes the following steps：
(1) extractant
A certain amount of acetonitrile is pipetted, with isopropanol, obtains the interior extraction solution for being designated as ethane nitrile content as 3mL/L, this solution
It should be now with the current；
(2) standard solution
A certain amount of standard substance is weighed in extractant, is accurate to 0.01mg, at least six standard solution is prepared, obtains moisture
Mass concentration is respectively 0,0.5,1.5,2.5,3.5, the series standard working solution of 5.0mg/mL, this solution should be now with the current.
(3) instrument and equipment
Assay balance：Sensibility reciprocal is 0.1mg；
Gas chromatograph：Equipped with thermal conductivity cell detector, recorder and integrator or other suitable data processing equipments；
Capillary chromatographic column：Internal diameter 0.53mm, 40.0 μm of film thickness, column length 30m.Stationary phase is bonding polystyrene-divinyl base
Benzene；
Gas chromatograph operating condition is as follows：
- carrier gas：Helium, constant current mode, flow 7mL/min；
- injector temperature：260℃；
- sampling volume：2μL；Split sampling, split ratio：5:1；
- column oven temperature program：170 DEG C of initial temperature keeps 4min；260 DEG C are risen to 90 DEG C/min rates, is kept
30min；
- detector temperature：260℃；Reference flow 20mL/min；Make-up gas flow 2mL/min；
(4) sample pre-treatments
Laboratory sample is extracted according to the sampling prescription that GB/T 5605 is provided according to experiment purpose or the sets itself methods of sampling is taken out
Take laboratory sample；Rear chamber is gentle puts for sample sealing, and detection was completed in 9 days；
5 filter sticks are randomly selected, weighs, is accurate to 0.1mg；Filter stick is longitudinally torn, then is laterally cut into 1~2cm long segments, is put
In 250mL conical flasks, 100mL extractants are added in, with 150r/min oscillation extraction 30min after sealing, take supernatant liquor mistake
The laggard gas chromatograph detection of 0.45 μm of organic phase filter membrane；The sample solution should complete machine analysis in 48h；
Tear initiation filter stick is answered to take out quick-fried pearl when cutting containing quick-fried pearl filter stick, then segment is put into conical flask and weighs；
(5) standard curve making
2 μ L standard solution is taken to inject gas chromatograph respectively, the peak height or peak area of moisture and internal standard compound is recorded, at least carries out two
Secondary measure；
The ratio of peak or peak area ratio of each standard solution moisture and internal standard compound are calculated, makes moisture concentration and ratio of peak or peak face
The relation curve of product ratio calculates regression equation, and regression curve related coefficient should be greater than 0.999；
The making of a standard curve is carried out per inspection lot；In addition, every 20 samples should inject an intermediate concentration mark after measuring
Quasi- solution if acquired results differ 5% with initial value, then should re-start the making of entire standard curve；
(6) blank test
Due to solvent absorption moisture, determination sample blank moisture moisture content is answered；Sample blank should use the method identical with sample
It extracted, analyzed；
(7) it measures
Sample extraction liquid and blank extract liquor are injected into gas chromatograph respectively, calculate peak area ratio or ratio of peak；
Replication twice, calculates the average value of parallel determination at identical conditions；
(8) result is calculated and is stated
With make the identical gas phase condition of working curve under, filter stick extract liquor after gas chromatographic analysis, calculate moisture with it is interior
Mark object peak height (or peak area) ratio, by regression equation calculation obtain extraction solution in moisture concentration, filter stick sample moisture content by
Following formula is calculated：
In formula：
W --- filter stick moisture content, unit %；
C1--- moisture concentration in extraction solution, unit are every milliliter of milligram；
C0--- moisture concentration in blank solution, unit are every milliliter of milligram；
V --- extraction liquor capacity, unit is milliliter；
M --- filter stick weight, unit are gram；
Take twice parallel determinations average value as final testing result, be accurate to 0.01%；
Parallel determinations relative deviation should be less than 5% twice.
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