卷烟气相燃烧产物的分析方法及分析系统技术领域 本发明涉及一种卷烟气相燃烧产物的分析方法及分析系统。 TECHNICAL FIELD cigarette gas analysis method and analysis of the combustion products  The present invention relates to a smoking combustion product gas analysis methods and analysis system. 背景技术 微炉式裂解器结构简单，炉腔温度分布均匀，性能可靠，使用广泛，被烟草行业大量采用。  Micro a furnace cracker simple structure, a uniform temperature distribution in the furnace chamber, reliable, widely used, the tobacco industry has been widely adopted. 目前在烟草行业该型号裂解器主要有两类应用:第一种为直接连接在气质联用谱仪(GC/MS)的气质联用汽化室前，作为在线裂解分析平台使用，方便可靠，结果重现性好。 The model is currently in the tobacco industry cracker there are two types of applications: the first one is directly connected before GC-MS spectrometer (GC / MS) GC-MS vaporizer, as cleavage online analysis platform, convenient and reliable results good reproducibility. 但由于普通毛细色谱柱在升温过程中不能接触含氧气氛，因此该系统不能实现有氧裂解，且进样量比较小。 However, due to the capillary column in the ordinary course of temperature rise is not in contact with an oxygen-containing atmosphere, so that the system can not achieve aerobic cleaved into smaller samples and ratio. 另一种是单独使用，使用冷阱捕集裂解产物，然后用有机溶剂将其洗脱，再用气质联用上机分析，属于离线裂解。 The other is used alone, a cold trap trapping lysate, which was then eluted with an organic solvent, and then spend machine GC analysis, are cleaved off. 此方法虽然样品量较在线裂解较大，而且可以实现有氧裂解，但通常捕集效率不高，溶剂洗脱不完全，重现性不尽如人意。 This method, although a larger sample volume than the cleavage line, cleavage and oxygen can be achieved, but generally not high collection efficiency, incomplete elution solvent, reproducibility is not satisfactory. 并且，以上两种方法只能捕集裂解产物全成分(包括粒相和气相)，而无法实现单独对裂解产物气相成分的收集和分析。 Further, the above two methods can trap lysate Ingredients (including particulate phase and gas phase), and can not be implemented separately collection and analysis of cleavage products of gas-phase constituents.  如图1所示，为SGE微炉式裂解器(PyrojectorII)主体结构示意图，包括进样器、进气腔10、裂解炉腔7、石英管6，石英管6内塞有石英棉，进样器包括进样杆1，进样杆I穿过进气腔10后与石英管6的一端相连，进气腔10的一侧与三通阀5的第一阀口连通，三通阀5的第二阀口与裂解气入口3连通，三通阀5的第三阀口与GC载气(一般为惰性气体)入口4连通，进气腔10的另一侧与吹扫出口2连通，石英管6位于裂解炉腔7内，石英管6的另一端伸出裂解炉腔7后用隔垫8密封，一GC进样针9的一端穿过隔垫8，裂解产物通过GC进样针9被导入气质联用谱仪(GC/MS)进行定性分析，该微炉裂解器可加装在气质联用汽化室前用作在线裂解，并且定性分析的裂解产物包括气相和粒相。  As shown, a furnace for the SGE micro-cracker (PyrojectorII) structural diagram of the body, including the injector, intake chamber 10, cracking furnace chamber 7, the quartz tube 61, the quartz tube with a quartz wool plug 6 , sample injector comprises a lever 1, sample I bar after passing through the intake chamber 10 is connected to one end of the quartz tube 6, the intake chamber 10 side of the three-way valve with a first port 5 communicates, three an inlet valve communicating with the second port 5 of the pyrolysis gas 3, the three-way valve with the third port GC carrier gas (usually an inert gas) inlet 4 communicates the intake 5 and the other side of the outlet chamber 10 is purged 2 communication, cracking the quartz tube 6 is located inside cavity 7, the other end of the quartz tube 6 extends the cracking furnace chamber 8 sealed by a spacer 7, an end of a GC syringe 9 through the spacer 8, into the cleavage product by GC 9 is introduced into the syringe for qualitative analysis by GC-MS spectrometer (GC / MS), the micro-cracking furnace may be installed in the GC cleavage product cleaved with the front line as the vaporization chamber, and qualitative analysis and gas-phase particles comprising .  申请号为200910172481.3的中国专利“一种对卷烟模拟燃烧产物的离线分析方法及装置”采用CDS热丝型裂解器(可程序升温)，模拟卷烟燃烧实际工况，收集裂解产物全成分(包括气相和粒相成分)，进行分析。 "Method and apparatus for off-line analysis of the combustion products of cigarettes analog"  Chinese Application No. 200910172481.3 patent using the hot wire type cracker CDS (programmable up), the actual combustion conditions simulated cigarette, lysates were collected Ingredients (including a gas phase and particulate phase components), were analyzed. 目前对于卷烟燃烧产物分析的技术和方法中，都只是针对裂解产物全成分(包括气相和粒相成分)的收集和分析，还不足以对烟气挥发性有机化合物的生成机理进行研究和探讨。 Current techniques and methods for the analysis of the combustion products in cigarettes, but are collected and analyzed for cleavage products Ingredients (including a gas phase and particulate phase components), not enough to generate volatile organic compounds of Flue Gas of research and discussion. 发明内容 本发明要解决的技术问题在于提供一种捕集烟叶在不同温度下的热裂解产物的气相成分，并对气相成分进行分析的卷烟气相燃烧产物的分析方法及分析系统。 SUMMARY OF THE INVENTION  The present invention is to solve the technical problem is to provide a trap tobacco pyrolysis products at different temperatures of the gas phase component, and gaseous phase component analysis method and analysis system for the combustion products of cigarettes gas phase analysis.  本发明的卷烟气相燃烧产物的分析方法，其包括以下步骤: I)将卷烟烟叶粉末至于含氧气体氛围下，进行等温裂解； 2)将等温裂解产物充分冷却； 3)冷却后的裂解产物通过剑桥滤片过滤，剑桥滤片将裂解产物中的粒相部分捕集，裂解产物中的气相部分穿过； 4)裂解产物中的气相部分进入吸附采样管，被吸附采样管吸附； 5)吸附采样管经热脱附后进入气质联用谱仪分析。  Analysis Cigarette gas according to the present invention, combustion products, comprising the steps of:  I) cigarette tobacco powder As an oxygen-containing atmosphere, an isothermal cleavage;  2) The isothermal lysate sufficiently cooled ;  3) cleavage product was cooled and filtered through a Cambridge filter, the Cambridge filter lysates particulate trap portion, the gas phase portion through lysate;  4) cleavage product of the gas phase analysis adsorption by thermal desorption sampling tube  5) into the GC-MS spectrometer; portion adsorption into the sampling tube, the sampling tube is adsorbed adsorption.  优选地,所述含氧气体为空气含9%氧气的氮气。  Preferably, the oxygen-containing gas is air containing nitrogen 9% oxygen.  优选地，所述剑桥滤片为有机黏合剂固定的玻璃纤维滤片。  Preferably, the organic binder is a Cambridge filter pad fixed glass fiber filter.  进一步地，所述剑桥滤片直径为44_，对直径大于0.1的颗粒物的捕集效率达到99.9%。  Further, the Cambridge filter having a diameter of 44_ collection efficiency of a diameter greater than 0.1 particles of 99.9%.  优选地，所述吸附采样管型号为西格玛奥德里奇公司生产的SUPELCO Carbotrap349。  Preferably, the adsorbent sampling tube model produced by Sigma-Aldrich SUPELCO Carbotrap349.  优选地，步骤I)中的裂解温度为300-900°C，吸附采样管的采样时间为2_5分钟。 Cracking temperature  Preferably, in step I) is 300-900 ° C, the adsorption sample tube for sampling time 2_5 minutes.  本发明还提供了一种卷烟气相燃烧产物的分析系统，包括一裂解器和与裂解器联用的配有挥发性有机物专用厚液膜毛细色谱柱的热脱附-气质联用谱仪，所述裂解器包括进样器、进气腔、裂解炉腔、石英管，所述进样器包括进样杆，所述进样杆穿过进气腔后与石英管的一端相连，所述石英管位于裂解炉腔内，所述石英管的另一端伸出裂解炉腔后与烟气捕集器的入口相连，所述烟气捕集器中设有剑桥滤片，所述烟气捕集器的出口与吸附气相的吸附采样管相连，吸附采样管与配有挥发性有机物专用厚液膜毛细色谱柱的联用。  The present invention further provides a gas analysis system for the combustion products of cigarettes, comprising a cracker with crackers and feature combined with volatile organic film thickness capillary column special thermal desorption - GC-MS spectra device, comprising the cleavage injector, intake chamber, cracking furnace chamber, a quartz tube, the injector comprising the injection rod into the quartz tube connected to one end of the sample bar through the intake chamber, the quartz tube positioned cracking furnace chamber, connected to the inlet of the flue gas after the trap to the other end of the quartz tube projecting cracking furnace chamber, the flue gas is provided Cambridge filter trap, the smoke adsorption gas outlet of the adsorption trap gas sampling pipe connected to the suction tube with the sampling of volatile organic compounds special thick film capillary column hyphenated.  优选地，所述石英管的另一端伸出裂解炉腔的长度为15_30mm以上。  Preferably, the other end of the quartz tube projecting length of cracking furnace chamber 15_30mm above.  优选地，所述进气腔的一侧为裂解气入口，所述进气腔的另一侧为吹扫出口。  Preferably, the intake chamber for the pyrolysis gas inlet side, the other side of the intake chamber is a purge outlet.  优选地，所述石英管和烟气捕集器之间通过聚四氟乙烯管相连，所述烟气捕集器和吸附采样管之间通过聚四氟乙烯管相连。  Preferably, the quartz tube is connected between the trap and the flue gas through a polytetrafluoroethylene tube, connected between the flue gas sampling tube and adsorbent trap pipe by polytetrafluoroethylene.  本发明的卷烟气相燃烧产物的分析方法，收集气相成分,研究气相有害成分形成机理，作为裂解机理研究的一部分。  Gas analysis method of the present invention a cigarette combustion products, to collect the gas phase components, harmful components in gas phase formation mechanism, as part of a study of the fragmentation mechanism. 并且，本发明的卷烟气相燃烧产物的分析系统，首次实现了对裂解产物气相成分的捕集，并对气相成分进行初步定性、定量分析，进而探索烟气有害成分形成机理，为卷烟降焦减害研究提供理论依据。 Further, the cigarette of the present invention gas phase combustion products analyzing system, for the first time the trap cleavage product gas phase component, the gas phase component and preliminary qualitative and quantitative analysis, and further explore the mechanism of formation of harmful components in flue gas, tar cigarette Save harm study provides a theoretical basis. 附图说明 图1为现有技术中SGE微炉式裂解器的主体结构示意图。 BRIEF DESCRIPTION  FIG. 1 is a schematic view of the main structure of the prior art micro SGE a furnace cracker.  图2为本发明的SGE微炉式裂解器的主体结构示意图。  The schematic structure of the main body 2 of the present invention. FIG micro SGE a furnace cracker.  图3为不同捕集时间对捕集效率的影响。  FIG. 3 is a different impact on the collection efficiency of the collection time.  图4为不同吸附采样管捕集效率比较。  Figure 4 compares the different adsorption capture efficiency sampling tube.  图5为烤烟样品裂解产物主要气相成分TIC图(裂解温度700°C )。  FIG 5 is a main sample lysate Tobacco gas-phase constituents of TIC (cracking temperature 700 ° C). 具体实施方式 以下结合附图对本发明的方案进一步说明。 DETAILED DESCRIPTION  The following figures further illustrate the present invention in conjunction with the program.  如图2所示，本发明的卷烟气相燃烧产物的分析系统，包括一裂解器和与裂解器联用的配有挥发性有机物(VOC)专用厚液膜毛细色谱柱的热脱附-气质联用谱仪(ATD-GC/MS)，该裂解器主体采用SGE微炉式裂解器(Pyrojectorll)，对其进行了改造，其包括进样器、进气腔10、裂解炉腔7、石英管6，进样器包括进样杆1，进样杆I穿过进气腔10后与石英管6的一端相连，石英管6位于裂解炉腔7内，石英管6的另一端伸出裂解炉腔7后与烟气捕集器4的入口相连，烟气捕集器4中设有剑桥滤片5，用以过滤裂解产物粒相成分，使得裂解产物中的气相成分通过，烟气捕集器4的出口与吸附气相的吸附采样管9相连，吸附采样管9与配有VOC专用厚液膜毛细色谱柱的热脱附-气质联用谱仪联用。  2, the cigarette of the present invention gas phase combustion products analyzing system, including a pyrolyzer and a cracker feature combined with thermal desorption of volatile organic compounds (VOC) in the special thick film capillary column - GC-MS spectrometer (ATD-GC / MS), the micro-cracker body using a furnace cracker SGE (Pyrojectorll), transformation was carried out, which comprises an injector, an intake chamber 10, cracking furnace chamber 7 quartz tube 6, the injector comprising an injection rod, sample I bar after passing through the intake chamber 10 is connected to one end of the quartz tube 6, 6 located within the quartz tube pyrolysis furnace cavity 7, the other end of the quartz tube 6 extends after the cracking furnace chamber 7 and the inlet 4 is connected to the flue gas trap, Cambridge filter 5 is provided in the flue gas trap 4, for filtering particulate component cleavage product, such that the gas phase component lysates by smoke 9 connected to the vapor outlet of the adsorption trap gas sampling tube 4 adsorption, adsorption and thermal desorption sampling tube 9 with a VOC of special thick film capillary column - GC-MS spectrometer linked with. 并且，石英管6的另一端伸出裂解炉腔7的长度为15-30_以上，便于裂解气流的冷却。 And, the other end of the quartz tube 6 extends the length of the cracking furnace chamber 7 is 15-30_ above, cleavage facilitate cooling air flow.  进气腔10的一侧为裂解气入口3，进气腔10的另一侧为吹扫出口2，其去掉原配的三通阀，改为一路气，使得裂解气同时充当载气的作用。  side of the intake chamber 10 of pyrolysis gas inlet 3, the other side of the intake chamber 10 is a purge outlet 2, which three-way valve wife removed, all the way to the air, so that the cracked gas simultaneously serves as a carrier gas role.  其中石英管6和烟气捕集器4之间通过聚四氟乙烯管(PTFE) 81相连，烟气捕集器4和吸附采样管9之间通过聚四氟乙烯管(PTFE)82相连，最大可能地避免对裂解产物尤其是其中气相成分的吸附。  wherein the quartz tube is connected to the flue gas trap between 6 and 4 via Teflon tubing (PTFE) 81, between the smoke trap 4 and the suction pipe 9 through the sampling tube of polytetrafluoroethylene (PTFE) 82 is connected to the maximum extent possible to avoid especially the adsorption of the cleavage product in which the gas phase component. [0031 ] 本发明的SGE微炉式裂解器，去除原有的GC进样针，将石英裂解管加长，伸出裂解炉腔一定的长度，便于裂解气流的冷却，并且去掉原配的三通阀，改为一路气，使得裂解气同时充当载气的作用，石英管伸出炉腔15〜30mm以上，避免裂解气流不能充分冷却而损坏剑桥滤片，进而降低粒相过滤效率。  SGE micro-cracker-type furnace according to the present invention, the removal of the original GC syringe, the lysed quartz tube extension, projecting a certain length cracking furnace chamber, to facilitate cooling of cracking gas stream, and removing the three-way valve wife , all the way to the air, so that the effect of pyrolysis gas simultaneously serves as a carrier gas, a quartz tube extending from the cavity 15~30mm above, the airflow can not be sufficiently cooled to avoid cracking and damage to the Cambridge filter, thereby reducing the particulate phase filtration efficiency.  本发明的剑桥滤片为直径44mm的有机黏合剂固定的玻璃纤维滤片，对于直径大于0.1 μ m的颗粒其捕集效率达99.9%，因此裂解产物经剑桥滤片之后基本为气相成分。  Cambridge filter sheet of the invention an organic binder 44mm diameter glass fiber filter sheet fixed, for the particle diameter greater than 0.1 μ m which collection efficiency of 99.9%, so after the cleavage product was substantially vapor Cambridge filter ingredient. 该剑桥滤片的介绍参考文献-《烟草-生产，化学和技术》，D.Layten Davis和MarkT.Nielsen, pp381。 Introduction References in the Cambridge filter - "Tobacco - Production, Chemistry and Technology", D.Layten Davis and MarkT.Nielsen, pp381.  本发明的吸附采样管为西格玛奥德里奇(Sigma Aldrich)公司生产的SUPELCOCarbotrap™系列市售商用不锈钢吸附采样管,具体选用carbotrap 349,对n_C3及以上的挥发性有机化合物有着较好的吸附效果。  Adsorption sampling tube according to the invention Sigma-Aldrich (Sigma Aldrich) produced SUPELCOCarbotrap ™ series commercially available commercial stainless steel sampling tube adsorption, specific choice carbotrap 349, of volatile organic compounds above n_C3 and has a better adsorption effect.  本发明对商用SGE微炉式裂解器进行改造，首次实现了对裂解产物气相成分的捕集，目前国内外尚无相关报道。  The present invention is a commercial micro SGE a furnace pyrolyzer transformation, the first time to capture the cleavage product gas phase component, there is no relevant reports at home and abroad. 改造后的SGE微炉式裂解器与配有VOC专用厚液膜毛细色谱柱的热脱附-气质联用谱仪(ATD-GC/MS)联用，可对不同温度下(300〜900°C )烟叶粉末的裂解产物气相成分进行定性、定量分析。 After transformation SGE micro-cracker with a furnace with a special thick film capillary column VOC thermal desorption - GC-MS spectrometer (ATD-GC / MS) in conjunction with, can be at different temperatures (300~900 ° C) cleavage product gas phase component tobacco powder qualitative and quantitative analysis. 该套系统及其分析方法的建立，将有助于进一步了解烟叶成分与烟气挥发性成分之间的关联，为深入研究卷烟烟气有害成分形成机理、推进降焦减害工作的开展提供必要的数据支撑。 The set of system and establish a method of analysis will help further understanding of the link between tobacco leaves and smoke volatile components, for further study of the formation mechanism of the harmful components of cigarette smoke, tar harm reduction work carried out to promote the necessary the data support.  本发明还提供了一种卷烟气相燃烧产物的分析方法，其包括以下步骤: I)打开与裂解器入口3相连的空气钢瓶，调整减压阀和流量计使裂解气气流量稳定在60 〜100ml/min ； 2)准确称取(2.0±0.l)mg烟叶粉末至进样器； 3)将裂解炉腔7内的裂解温度调整到700°C ； 4)当裂解温度稳定后，压下进样杆1，使得卷烟烟叶粉末进入石英管6内，置于含氧气体(空气或含9%氧气的氮气)的氛围下，进行等温裂解； 5)裂解产物经过加长的石英管6充分冷却； 6)冷却后的裂解产物通过剑桥滤片5过滤，剑桥滤片5将裂解产物中99.9%的的粒相部分捕集，裂解产物中的气相部分穿过； 7)裂解产物中的气相部分进入吸附采样管9，被吸附采样管9吸附； 8)从压下进样器推杆开始计时，经过一定时间如2-5分钟后，拔去吸附采样管9 ； 9)吸附采样管9与配有  The present invention further provides a method for analyzing gas-phase combustion products of cigarettes, comprising the steps of:  I) an inlet opening and cracker air cylinder 3 is connected to adjust the pressure reducing valve and flow meter so that cracking gas Gas flow stability in 60 ~100ml / min;  2) accurately weighed (2.0 ± 0.l) mg to tobacco powder injector;  3) the cracking temperature within the cracking furnace chamber 7 is adjusted to 700 ° C;  4) when the temperature was stabilized after lysis, the sample lever 1 is depressed, so that the cigarette tobacco powder into the quartz tube 6, is placed under atmosphere of an oxygen-containing gas (air or nitrogen, with 9% oxygen) is performed isothermal cleavage;  5) cleavage product through a quartz elongated tube 6 is sufficiently cooled;  6) cleavage product after cooling by a Cambridge filter 5 filters, Cambridge filter 5 lysates 99.9% of the particulate phase trap section, the gas phase portion through the lysate; gas phase portion  7) the lysate sampling tube 9 enters the adsorption, the adsorption is adsorbed sampling tube 9;  8) reduction from the injector plunger start time, such as after a certain time after 2-5 minutes, pulling adsorption sampling tube 9;  9) has the suction with the sampling tube 9 VOC (挥发性有机物)专用厚液膜毛细色谱柱的热脱附-气质联用谱仪联用，经热脱附后进入GC/MS分析。 VOC (volatile organic compounds) thick film capillary column dedicated thermal desorption - GC-MS spectrometer combined with, by thermal desorption into the GC / MS analysis.  按照上述方法，对某烤烟样品进行了分析，通过捕集烟叶在不同温度有氧条件下的热裂解产物气相成分，对其进行初步定性、定量分析，进而探索烟气有害成分形成机理，为卷烟降焦减害研究提供理论依据。  According to the above method, a Tobacco samples were analyzed by trapping tobacco pyrolysis product gas phase component aerobic conditions at different temperatures, and subjected to a preliminary qualitative and quantitative analysis, and further explore the mechanism of formation of harmful components in flue gas , cigarette tar harm reduction study provides a theoretical basis. 上述方法中，首先对捕集时间以及吸附采样管9进行了优化，具体如下: 1、捕集时间对捕集效率的影响 见图3所示，不同捕集时间下的峰面积值，由图3可知，2min的捕集时间已经能够完全捕集裂解产物的气相成分，因此本发明方法中的捕集采样时间定为2min。 In the above method, first, the collection time and an adsorption sample tube 9 is optimized, as follows:  1, the influence on the collection efficiency of the collection time  shown in Figure 3, at different times of capturing peak area, seen in FIG. 3, 2min time been able to fully capture and trap gas component cleavage products, thus capturing the sampling time in a given process of this invention is 2min.  2、吸附采样管的选择 根据装填吸附剂的种类和方式，可将吸附采样管分为单一型和复合型两种。  2, the sampling tube adsorption selected  depending on the type and manner of loading of the adsorbent, the adsorption sample tube may be divided into two kinds of single and compound type. 吸附剂比表面积越大，其吸附能力越强。 The larger the specific surface area of the adsorbent, the adsorption capacity stronger. 由于裂解产物气相成分复杂，被测物质的沸程范围很宽，所以采用三段复合型吸附采样管进行捕集。 Since the gas phase component complex lysate, the test substance boiling range is wide, so a three-stage composite adsorbent trap sample tube. 目前已商品化的三段复合型吸附采样管主要有carbotrap300, carbotrap317和carbotrap 349等型号，各自组成和比表面积如下表I所示。 Has been the commercialization three sections composite adsorbent sampling tube main carbotrap300, carbotrap317 carbotrap 349 and other models, their composition and specific surface area shown in Table I below.  表I吸附采样管比表面积和吸附剂组成  Table I adsorption specific surface area of the sampling tube and sorbents 
 分别将相同的烟末样品按卷烟气相燃烧产物的分析方法，并引入上述三种吸附采样管进行气体吸附采样，利用ATD-GC/MS测定吸附采样管的捕集能力。  The same end, respectively, by the cigarette smoke gas phase combustion of the sample analysis of the product, and introduces the three adsorption gas adsorption sample tube sampling, the sampling tube was measured trapping ability by adsorption ATD-GC / MS. 检测结果如图4所示，该结果表明，与理化性质相对应，三种吸附采样管对丙烯腈，苯，甲苯和苯乙烯等较高沸点的物质具有基本相同的吸附能力:carbotrap317和carbotrap349两种吸附采样管对I,3- 丁二烯和异成二烯的捕集能力基本一致，但均高于carbotrap300。 The detection results shown in Figure 4, the results show that the physical and chemical properties corresponding to the three sampling tube having substantially the same adsorption ability of adsorbing acrylonitrile, benzene, toluene, styrene, and other high boiling materials: carbotrap317 and two carbotrap349 sampling tube to adsorb species I, 1,3-butadiene and iso-trapping ability to diene consistent, but higher than carbotrap300. 综合考虑性价比,选择carbotrap 349吸附采样管捕集裂解产物气相成分。 Considering the cost, adsorption carbotrap 349 select the sampling tube trap lysate gaseous phase component.  本发明中使用的配有V0C(挥发性有机物)专用厚液膜毛细色谱柱的热脱附-气质联用谱仪(ATD-GC/MS)联用仪器参数如表2所示，本发明卷烟气相燃烧产物的分析系统的裂解试验条件如表3所示。  with V0C (volatile organic compounds) for the film thickness of the thermal desorption of the capillary columns used in the present invention - GC-MS spectrometer (ATD-GC / MS) associated with the instrument parameters as shown in Table 2, test conditions system cleavage cigarette gas combustion products of the present invention as shown in table 3.