CN105004819B - A kind of method of hydrogen cyanide content in measure cigarette mainstream flue gas - Google Patents
A kind of method of hydrogen cyanide content in measure cigarette mainstream flue gas Download PDFInfo
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- CN105004819B CN105004819B CN201510507625.1A CN201510507625A CN105004819B CN 105004819 B CN105004819 B CN 105004819B CN 201510507625 A CN201510507625 A CN 201510507625A CN 105004819 B CN105004819 B CN 105004819B
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Abstract
The invention discloses a kind of while the method that traps gas phase and grain phase hydrogen cyanide in cigarette mainstream flue gas, the method is using the hydrogen cyanide in the trapping main flume of the glass fiber filter containing soluble cupric salt.The capturing device of the method is simple, method of operating is easy, measurement result is accurate, saves the test period.
Description
Technical field
The invention belongs to cigarette mainstream flue gas detection field, and in particular in a kind of measure cigarette mainstream flue gas, hydrogen cyanide contains
Amount method.
Background technology
Hydrogen cyanide (HCN) is one of important environmental contaminants, its mechanism of toxication predominantly cryanide ion and oxidized form cell
Ferric iron in chromo-oxidase is combined, and has blocked ferric electron transmission in oxidizing process, prevent biological tissue cell from
Using oxygen, stop up in formation, go into a coma, breathing stopping, serious is dead in several minutes.Hydrogen cyanide in cigarette mainstream flue gas is main
Come from the conversion of nitrogen-containing compound in tobacco, its content is low and is oxidized easily degraded, and cigarette smoke composition is complicated, therefore
The content for how determining hydrogen cyanide in cigarette mainstream flue gas always is the work of rich challenge.
In cigarette mainstream flue gas, the hydrogen cyanide of about 50 mass % is present in granule phase substance, and remaining hydrogen cyanide is present in gas gas-phase objects
In.The international body such as country's tobacco business, HEALTH CANADA generally traps total particulate matter in mainstream smoke using cambridge filter at present
Hydrogen cyanide, while using NaOH-ethylenediamine solution trapping main flume gas gas-phase objects hydrogen cyanide.The method equipment therefor is as schemed
Shown in 1, wherein cigarette 1 is connected with trap 2, equipped with the Cambridge for being used for trapping grain phase hydrogen cyanide in main flume in trap 2
Filter disc.Trap 2 is connected with collecting trap 4 by connecting line 3, is contained with NaOH-ethylenediamine solution in collecting trap 4, should
NaOH-ethylenediamine solution is used for trapping gas phase hydrogen cyanide in main flume.Collecting trap 4 is single with suction by connecting line 5
Unit 6 is connected.Above-mentioned capture method needs first to trap the granule phase substance hydrogen cyanide and gas gas-phase objects hydrogen cyanide in main flume, then obtains respectively
Obtain two kinds of solution to be measured of grain phase eluent and gas phase adsorption liquid.AAS is respectively adopted after the two derivatization to be measured.
Party's subtraction unit complexity, pre-treatment and detection process are loaded down with trivial details, workload is big.
Prior art also needs to the method for preferably determining hydrogen cyanide content in cigarette mainstream flue gas.
Content of the invention
One aspect of the present invention provide a kind of and meanwhile trap cigarette mainstream flue gas in gas phase and grain phase hydrogen cyanide method.This
Bright another aspect provides a kind of method for determining hydrogen cyanide content in main flume.
First aspect present invention provide a kind of and meanwhile trap cigarette mainstream flue gas in gas phase and grain phase hydrogen cyanide method, should
Method is using the hydrogen cyanide in the glass fiber filter trapping main flume containing soluble cupric salt.
In a specific embodiment, the capture method of aforementioned any one of the invention, the soluble cupric salt is
One or more selected from following material：Copper sulphate, copper sulfate hydrate, copper chloride, chlorination copper hydrate, copper nitrate, nitric acid
Copper hydrate, copper acetate, acetic acid copper hydrate.
In a specific embodiment, the capture method of aforementioned any one of the invention, per 15cm2Described containing solubility
In the glass fiber filter of cupric salt, the content of copper is 0.001～0.5mmol, preferably 0.2～0.3mmol.
In a specific embodiment, the capture method of aforementioned any one of the invention, wherein described containing soluble two
The glass fiber filter of valency mantoquita is prepared as follows：Cupric salt solution is put on glass fiber filter, is then dried in the air
Dry, the glass fiber filter is balanced certain time with a temperature of in suitable relative humidity using front；
Relative humidity is preferably 60% ± 2%, and temperature is preferably 22 ± 1 DEG C, and equilibration time is preferably 48 hours；
Preferably, in the cupric salt solution, the concentration of copper ion is 10-3～10-1mol/L；
Preferably, per 15cm2On glass fiber filter apply cupric salt solution amount be 1～5ml, preferably 2～
3ml.
Before experiment, first by the glass fiber filter containing soluble cupric salt in suitable temperature and humidity (humidity
For 60% ± 2%, 22 ± 1 DEG C of temperature) environment in balance the suitable time (such as 48h) after, filter disc contains a certain amount of water
Point.It is additionally, since in flue gas, filter disc moisture and flue gas moisture is anti-with hydrogen cyanide collectively as copper ion
Answer medium.Soluble copper salt can be dissolved in filter disc and flue gas in moisture, and produce copper ion, so as to there is chemistry with hydrogen cyanide
Reaction, realizes trapping effect.
In a specific embodiment, the capture method of aforementioned any one of the invention, wherein described glass fiber filter
For cambridge filter, the such as cambridge filter of a diameter of 44mm or 92mm, the preferably cambridge filter of diameter 44mm.It is computed, directly
The area of the cambridge filter of footpath 44mm is for about 15cm2.
Second aspect present invention provides a kind of assay method of hydrogen cyanide content in cigarette mainstream flue gas, and the method is using this
Invent the hydrogen cyanide in the capture method trapping main flume of aforementioned any one.
In a specific embodiment, the assay method of aforementioned any one of the invention, the method are comprised the following steps
One or multi-step：
1) using the hydrogen cyanide in the capture method trapping main flume of aforementioned any one of the invention, obtaining trapping has cyaniding
The glass fiber filter of hydrogen；
2) eluting trapping with the KOH aqueous solution has the glass fiber filter of hydrogen cyanide, obtains hydrogen cyanide eluent；
3) hydrogen cyanide content in hydrogen cyanide eluent is determined；
4) hydrogen cyanide content in every cigarette mainstream flue gas is calculated；
It is preferred that adopting quantified by external standard method.
In a specific embodiment, the assay method of aforementioned any one of the invention, wherein step 3) use ion color
Spectrometry determines the hydrogen cyanide content in hydrogen cyanide eluent；
Preferably, the chromatography of ions is suppressed ion chromatography, suppresses electric current to be preferably 170～190 μ A, more excellent
Elect 179 μ A as.
In a specific embodiment, the assay method of aforementioned any one of the invention, the parameter of the chromatography of ions
It is selected from following one or more：
A) ion column temperature：25～35 DEG C, preferably 30 DEG C；
B) flow velocity：1.1～1.5mL/min, preferably 1.2mL/min；
C) sampling volume：20～30 μ L, preferably 25 μ L；
D) mobile phase：The KOH aqueous solution；
Preferably, KOH aqueous solution rinse procedures are as follows：
0～20min, KOH concentration is 5mmol/L,
20～20.1min, KOH concentration is 10mmol/L,
20.1～25.1min, KOH concentration is 60mmol/L,
25.1～～28.1min, KOH concentration are 5mmol/L.
Unless stated otherwise：
Heretofore described soluble cupric salt is water soluble or soluble in water, and produces one after being dissolved in water in water
Determine the Cu of concentration2+The cupric salt of ion.
Heretofore described solution is the aqueous solution.
According to carrying out by national Specification the step of be not explicitly defined in present invention experiment.
The beneficial effect of patent of the present invention
The present invention is using the cambridge filter containing soluble cupric salt, while trapping the granule phase substance cyaniding in main flume
Hydrogen and gas gas-phase objects hydrogen cyanide, the cyanogen after trapping is had hydrogen cyanide cambridge filter through KOH solution wash-out, in single-time measurement eluent
Change hydrogen content, calculate the hydrogen cyanide content obtained in cigarette mainstream flue gas.Conventional method is compared, the inventive method has following excellent
Point：
(1) capturing device is simple, need not connect collecting trap；
(2) measuring process is simple, and the present invention is without the need for processing to granule phase substance in main flume and gas gas-phase objects hydrogen cyanide respectively.This
Inventive method disposably traps granule phase substance hydrogen cyanide and gas gas-phase objects hydrogen cyanide in main flume, and the disposable hydrogen cyanide that obtains is eluted
Liquid, the hydrogen cyanide content in disposable detection eluent.Compared with other methods of prior art, the inventive method operation letter
Just, the test period is shortened.
(3) present invention is using gas phase and grain phase in the glass fiber filter trapping main flume containing soluble cupric salt
Hydrogen cyanide.During cigarette smoking, flue gas is by the flow of filter disc big (35mL/s) and time short (2s), glass of the present invention
Fiber filter disc can either effectively adsorb the granule phase substance in main flume, additionally it is possible to fully send out with gas phase hydrogen cyanide in main flume
Raw complex reaction, so that realize the abundant trapping to gas phase in main flume and grain phase hydrogen cyanide.
(4) present invention elutes the hydrogen cyanide on glass fiber filter using KOH solution, as ion chromatograph is generally carried
KOH automatic generators, therefore separately need not prepare KOH solution, simplify testing process.
(5) accurately, the present invention is using the hydrogen cyanide content in sulfate by ion chromatography eluent, and optimizes for measurement result
Chromatography of ions parameter, the measurement result degree of accuracy are high.
(6) capture rate is high, and the inventive method is to the capture rate of gas phase and grain phase hydrogen cyanide in the checking of cigarette main flow up to 99%
More than, capture rate is high.
In sum, the inventive method simplifies hydrogen cyanide capturing device and step and optimizes detecting step, not only carries
High arresting efficiency, shortens the pre-treatment time, and method is easy.The inventive method has higher application and promotional value.
Description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the application.Attached
In figure：
Fig. 1 is the schematic device that prior art traps hydrogen cyanide in main flume；
Fig. 2 is the schematic device that embodiment 1 traps hydrogen cyanide in main flume.
Specific embodiment
Below by drawings and Examples, technical scheme is described in further detail.The present invention shows
Meaning property embodiment and its illustrated for explaining the present invention, does not constitute limitation of the invention.
Embodiment 1～3
1) reagent and instrument used by
Reagent：Hydrogen cyanide standard substance solution, copper sulphate, KOH, Kentucky 3R4F reference samples, ultra-pure water；
Instrument：Ion chromatograph (is equipped with column oven, gradient pump, anion suppressor, KOH generators and Conductivity detection
Device), pump unit (SM450 smoking machines), balance, supersonic generator, pure water meter, 0.45 μm of water phase filter membrane, the disposable pins of 5mL
Cylinder, Φ 44mm cambridge filters (whatman F319-04).
2) prepared by filter disc：CuSO is pipetted using liquid-transfering gun4Solution (the CuSO of embodiment 1～34The concentration and volume of solution is such as
Shown in table 1), pipette tips aligns filter hair side center, CuSO4Solution is vertically at the uniform velocity instilled in filter disc, and filtrate is from filter disc center to side
Along diffusion, after dripping, filter surface is moistened and slightly light blue.After drying, filter surface is dried and slightly light blue, explanation
There is the hydrate of copper sulphate in the filter surface after drying.
1 CuSO of table4The concentration and volume of solution
| Embodiment is numbered | V(CuSO4)/mL | c(CuSO4)/mol/L |
| 1 | 2 | 0.1 |
| 2 | 3 | 0.05 |
| 3 | 1 | 0.1 |
3) cigarette sample prepares and samples：3R4F cigarette samples and the above-mentioned cambridge filter for drying are placed in 22 DEG C ± 1 DEG C
With balance 48h in environment of the relative humidity for 60% ± 2%, filter disc balance 48h in environment of the relative humidity for 60% ± 2%
Afterwards, filter disc contains moisture.
According to GB/T5606.1-2004 (cigarette part 1s：Sampling) extract cigarette sample.
4) in cigarette mainstream flue gas hydrogen cyanide trapping：Fig. 2 illustrates the schematic diagram of capturing device of the present invention.As shown in Fig. 2
By step 3) in obtain balance after cambridge filter load trap 2 in.By step 3) cigarette sample 1 that obtains and trap
2 connections, the other end of trap 2 connect pump unit 6 (SM450 smoking machines) by connecting line 3, according to YC/T 253-
2008 (the measure continuous flow method of hydrogen cyanide in cigarette mainstream flue gas) standard conditions smoking cigarette, often wheel suction 4, while catch
The hydrogen cyanide of gas phase and grain phase in collection cigarette sample main flume.
5) pre-treatment of sample：After suction is finished, cambridge filter is taken out from trap, be put in 100mL conical flasks, make
It is put in above-mentioned conical flask after trap protecgulum inwall is wiped with a quarter filter disc, adds 50mL 0.01mol/L KOH molten
Liquid, ultrasound wash-out 30min, eluent is transferred in 100mL volumetric flasks, and is settled to quarter with 0.010mol/L KOH solutions
Degree, obtains hydrogen cyanide eluent.About 10mL eluents are taken with syringe, is loaded in sample feeding pipe with after 0.45 μm of water phase membrane filtration.
6) quantitative analysis：The hydrogen cyanide content in above-mentioned hydrogen cyanide eluent is detected using ion chromatograph, using external standard
Standard measure, concrete grammar are as follows：
Prepared by 6.1 standard liquids：The CN of 1mL variable concentrations is added in 50mL volumetric flasks-0.010mol/L KOH molten
Liquid, then with 0.01mol/L KOH solution constant volume scales, is prepared into standard liquid, CN-Concentration is respectively 0.5mg/L, 1.0mg/
L、5.0mg/L、10.0mg/L、50.0mg/L.
6.2 detect above-mentioned standard solution using ion chromatograph, with corresponding CN-Concentration (mg/L) is abscissa, and which responds
Peak area is ordinate, draws calibration curve.Chromatography of ions condition is as follows：
Column temperature：30℃；Flow velocity：1.2mL/min；Suppressor electric current：179mA；Sampling volume：25μL；Mobile phase：KOH water
Solution leacheate program such as table 2.
2 KOH aqueous solution leacheate programs of table
| Time (min) | KOH concentration (mmol/L) |
| 0 | 5 |
| 6 | 5 |
| 20 | 10 |
| 20.1 | 60 |
| 25 | 60 |
| 25.1 | 5 |
| 28.1 | 5 |
Regression equation is measured for Y=0.0097+0.1841X, coefficient correlation is 0.9994.
The hydrogen cyanide eluent of the 6.3 chromatography of ions condition detection steps 5 for pressing step 6.2, and response peak area will be determined
Calibration curve is substituted into, CN in hydrogen cyanide eluent is obtained-Concentration.
6.4 CN measured according to step 6.3-Concentration, the hydrogen cyanide content in every cigarette is calculated by following formula：
Wherein m is the content (unit of hydrogen cyanide in every cigarette：μ g/cig), CNs of the c for hydrogen cyanide eluent-Concentration
(unit：μ g/mL), volume (units of the v for hydrogen cyanide eluent constant volume：ML), 27.03 is the molecular weight of hydrogen cyanide, and 26.02 are
CN-Molecular weight, n be suction cigarette number.
It is computed, hydrogen cyanide content such as table 3 in the main flume of the Kentucky 3R4F reference cigarette for measuring embodiment 1～3
Shown.
The hydrogen cyanide content of 3 embodiment 1～3 of table
| Embodiment is numbered | 1 | 2 | 3 |
| Hydrogen cyanide content (μ g/cig) | 103.0 | 105.5 | 102.1 |
Comparative example 1
Kentucky 3R4F reference cigarette is tested using industry standard methods (YC/T 253-2008), test result is
106.2μg/cig.
As shown in table 4, the test result deviation of method of testing of the present invention and industry standard methods is not more than 4%, 1%～
Between 4%, show that the method for the present invention is coincide with both industry standard methods good.
4 embodiment 1～3 of table and the hydrogen cyanide content and standard deviation of comparative example 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Hydrogen cyanide (μ g/cig) | 103.0 | 105.5 | 102.1 | 106.2 |
| SD | 3% | 1% | 4% | -- |
The measure of 4 rate of recovery of embodiment
With 3 groups of Kentucky 3R4F reference cigarette as object, the cyaniding in its main flume is trapped using the method for embodiment 1
Hydrogen.After suction trapping is finished, cambridge filter is taken out from trap, be put in 100mL conical flasks, using a quarter filter disc
It is put in above-mentioned conical flask after wiping trap protecgulum inwall, adds 50mL 0.010mol/L KOH solutions, also adds simultaneously respectively
Enter the CN- solution of basic, normal, high 3 kinds of concentration gradients, ultrasound wash-out 30min is transferred to eluent in 100mL volumetric flasks, is used in combination
0.010mol/L KOH solutions are settled to scale, obtain the mark-on solution of 3 groups of hydrogen cyanide eluents, and are built according to embodiment 1
Vertical ion chromatographic method is detected.As a result it is listed in the table below as shown in table 5, the rate of recovery of this method is in 93.4%-102.2%
Between, meet the requirement of quantitative analysis：
The recovery of standard addition of 5 embodiment 4 of table
The measure of 5 capture rate of embodiment
1) reagent and instrument used by：With embodiment 1
2) prepared by filter disc：With embodiment 1
3) cigarette sample prepares and samples：With embodiment 1
4) in cigarette mainstream flue gas hydrogen cyanide trapping：Cyanogen in main flume is determined using prior art as shown in Figure 1
The device for changing hydrogen content determines capture rate.As shown in figure 1, by step 3) in cambridge filter after the balance that obtains load trap
In 2, for trapping grain phase and gas phase hydrogen cyanide in main flume.Trap 2 is connected with collecting trap 4 by connecting line 3, trapping
NaOH-ethylenediamine solution is contained with trap 4, the NaOH-ethylenediamine solution is used for trapping residual in main flume
Hydrogen cyanide.Collecting trap 4 is connected with pump unit 6 by connecting line 5.According to YC/T 253-2008 (cyanogen in cigarette mainstream flue gas
Change the measure continuous flow method of hydrogen) standard conditions smoking cigarette, often wheel suction 4, while trap in cigarette sample main flume
Gas phase and the hydrogen cyanide of grain phase.
5) pre-treatment of sample：After suction is finished, cambridge filter is taken out from trap, be put in 100mL conical flasks, make
It is put in above-mentioned conical flask after trap protecgulum inwall is wiped with a quarter filter disc, adds 50mL 0.010mol/L KOH molten
Liquid, ultrasound wash-out 30min, eluent is transferred in 100mL volumetric flasks, and is settled to quarter with 0.010mol/L KOH solutions
Degree, obtains hydrogen cyanide eluent.About 10mL eluents and trapping solution are taken respectively with syringe, is loaded with 0.45 μm of water phase membrane filtration
In sample feeding pipe.
6) quantitative analysis：By calibration curve regression equation and the chromatography of ions condition of embodiment 1, detecting step cyaniding 5)
Hydrogen eluent and NaOH-ethylenediamine trapping solution, and response peak area substitution calibration curve will be determined, obtain hydrogen cyanide and wash
CN in de- liquid and NaOH-ethylenediamine trapping solution-Concentration.
It is computed, measures the CN in sample eluent-Concentration be 7.93mg/L, remain in NaOH-ethylenediamine and catch
CN in collection solution-Concentration minimum, be 0.07mg/L.Above-mentioned test confirmation, the grain phase and gas phase hydrogen cyanide in main flume
Trapped by the cambridge filter containing soluble cupric salt, capture rate is 7.93/ (7.93+0.07)=99.125%, reaches
More than 99%.
Finally it should be noted that：Above example is only in order to illustrating technical scheme rather than a limitation；To the greatest extent
Pipe has been described in detail to the present invention with reference to preferred embodiment, and those of ordinary skill in the art should be understood：Still
The specific embodiment of the present invention can be modified or equivalent is carried out to some technical characteristics；Without deviating from this
The spirit of bright technical scheme, its all should cover in the middle of the technical scheme scope that the present invention is claimed.
Claims (20)
1. a kind of while the method that traps gas phase and grain phase hydrogen cyanide in cigarette mainstream flue gas, the method is using containing soluble two
Hydrogen cyanide in the glass fiber filter trapping main flume of valency mantoquita；
The glass fiber filter containing soluble cupric salt is prepared as follows：Cupric salt solution is put on glass
On glass fiber filter disc, then dry, the glass fiber filter is balanced necessarily in suitable relative humidity with a temperature of using front
Time, the relative humidity are 60% ± 2%, and the temperature is 22 ± 1 DEG C.
2. the capture method of claim 1, the soluble cupric salt are selected from one or more of following material：Sulfuric acid
Copper, copper sulfate hydrate, copper chloride, chlorination copper hydrate, copper nitrate, nitric acid copper hydrate, copper acetate, acetic acid copper hydrate.
3. the capture method of claim 1, per 15cm2Copper in the glass fiber filter containing soluble cupric salt
Content be 0.001～0.5mmol.
4. the capture method of claim 1, per 15cm2Copper in the glass fiber filter containing soluble cupric salt
Content be 0.2～0.3mmol.
5. the capture method of claim 1, the time of balance is 48 hours.
6. the capture method of claim 1, in the cupric salt solution, the concentration of copper ion is 10-3～10-1mol/L.
7. the capture method of claim 1, per 15cm2The amount of the cupric salt solution applied on glass fiber filter is 1～5ml.
8. the capture method of claim 1, per 15cm2The amount of the cupric salt solution applied on glass fiber filter is 2～3ml.
9. the capture method of any one of claim 1-8, wherein described glass fiber filter are cambridge filter.
10. the capture method of any one of claim 1-8, cambridge filter of the wherein described glass fiber filter for diameter 44mm.
The assay method of hydrogen cyanide content in a kind of 11. cigarette mainstream flue gas, the method usage right require 1～10 any one
Hydrogen cyanide in capture method trapping main flume.
The assay method of 12. claims 11, the one or multi-step that the method is comprised the following steps：
1) usage right requires the hydrogen cyanide in the capture method trapping main flume of 1～5 any one, and obtaining trapping has hydrogen cyanide
Glass fiber filter；
2) eluting trapping with the KOH aqueous solution has the glass fiber filter of hydrogen cyanide, obtains hydrogen cyanide eluent；
3) hydrogen cyanide content in hydrogen cyanide eluent is determined；
4) hydrogen cyanide content in every cigarette mainstream flue gas is calculated.
The assay method of 13. claims 12, the method adopt quantified by external standard method.
The assay method of 14. claims 12, wherein step 3) using the cyaniding in ion-chromatographic determination hydrogen cyanide eluent
Hydrogen content.
The assay method of 15. claims 14, the chromatography of ions are suppressed ion chromatography.
The assay method of 16. claims 15, the suppression electric current of suppressed ion chromatography is 170～190 μ A.
The assay method of 17. claims 15, the suppression electric current of suppressed ion chromatography is 179 μ A.
The assay method of 18. any one of claim 14～17, the parameter of the chromatography of ions are selected from following one or more：
A) ion column temperature：25～35 DEG C；
B) flow velocity：1.1～1.5mL/min；
C) sampling volume：20～30 μ L；
D) mobile phase：The KOH aqueous solution.
The assay method of 19. claims 18, the parameter of the chromatography of ions are selected from following one or more：
A) ion column temperature：30℃；
B) flow velocity：1.2mL/min；
C) sampling volume：25μL.
The assay method of 20. claims 18, mobile phase KOH aqueous solution rinse procedures are as follows：
0～20min, KOH concentration is 5mmol/L,
20～20.1min, KOH concentration is 10mmol/L,
20.1～25.1min, KOH concentration is 60mmol/L,
25.1～～28.1min, KOH concentration are 5mmol/L.
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| CN105866351A (en) * | 2016-05-31 | 2016-08-17 | 安徽中烟工业有限责任公司 | Method for quickly measuring harmful ingredients in main stream smoke of cigarette |
| CN108402513A (en) * | 2018-04-26 | 2018-08-17 | 河北中烟工业有限责任公司 | A kind of scavenging conduit for the detection of cigarette purge and trap |
| CN110895231B (en) * | 2019-12-26 | 2022-08-19 | 贵州中烟工业有限责任公司 | Method for measuring moisture in aerosol of heated non-combustible cigarette |
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| CN103616452A (en) * | 2013-12-06 | 2014-03-05 | 中国烟草总公司郑州烟草研究院 | Determination method for experiment of simulating cigarette burning for generating hydrogen cyanide |
| CN103611505B (en) * | 2013-12-06 | 2015-07-08 | 中国烟草总公司郑州烟草研究院 | Preparation method, product and application of copper ion functionalized porous cellulose composite microsphere |
| CN203597391U (en) * | 2013-12-06 | 2014-05-21 | 中国烟草总公司郑州烟草研究院 | Composite filter tip with copper ion functionalization porous cellulose composite microsphere |
| CN103776972A (en) * | 2014-02-21 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Method for determining filter tip entrapment quantity of hydrogen cyanide in main stream smoke of cigarettes |
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