CN103115956A - Low-pressure high-temperature pyrolysis furnace applicable to mass spectrographic analysis and application thereof - Google Patents
Low-pressure high-temperature pyrolysis furnace applicable to mass spectrographic analysis and application thereof Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 81
- 238000004458 analytical method Methods 0.000 title description 4
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 238000005070 sampling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000003245 coal Substances 0.000 description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000534 ion trap mass spectrometry Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
一种适合质谱分析的低压高温热解炉及其应用，该热解炉由炉体、支架、热解室、进样管和差分孔组成；其通过热解室直接与质谱电解室相连，控制热解炉温度，使样品在不同温度下热解，由于电离室处于真空状态，而热解炉内为低压，因此热解产物会因为压力作用向电解室扩散，使样品热解产物第一时间进入电解室被电离，解决了低压热解反应中自由基和不稳定中间体难以被原位检测的问题。
A low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis and its application. The pyrolysis furnace is composed of a furnace body, a support, a pyrolysis chamber, a sample injection tube and a differential hole; The temperature of the pyrolysis furnace allows the sample to be pyrolyzed at different temperatures. Since the ionization chamber is in a vacuum state and the pyrolysis furnace is at low pressure, the pyrolysis products will diffuse to the electrolysis chamber due to the pressure, so that the pyrolysis products of the sample will be dissipated immediately. It enters the electrolysis chamber and is ionized, which solves the problem that free radicals and unstable intermediates are difficult to be detected in situ in low-pressure pyrolysis reactions.
Description
技术领域technical field
本发明涉及一种热解炉，具体涉及一种适合质谱分析的低压高温热解炉及其应用。The invention relates to a pyrolysis furnace, in particular to a low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis and its application.
背景技术Background technique
煤的热解作用是煤利用过程中的一个重要工艺技术，对煤热解过程和产物的研究有助于加深了解煤的结构和组成，可以帮助分析热解行为对整个气化过程的影响，因此，充分认识煤的热解过程可进一步的阐明煤的分子结构。The pyrolysis of coal is an important technology in the process of coal utilization. The study of coal pyrolysis process and products can help to deepen the understanding of coal structure and composition, and can help analyze the impact of pyrolysis behavior on the entire gasification process. Therefore, fully understanding the coal pyrolysis process can further clarify the molecular structure of coal.
质谱技术是一种测量离子荷质比的分析方法，其原理是使试样中各组分在离子源中发生电离，生成不同荷质比的带正电荷的离子，经加速电场的作用，形成离子束，进入质量分析器。在质量分析器中，再利用电场和磁场使发生相反的速度色散，将它们分别聚焦而得到质谱图，从而确定其质量。目前常用的质谱技术有四级杆质谱、离子阱质谱、飞行时间质谱等等。其中四级杆质谱是利用不同质量的离子，在射频场中运动轨迹的不同来分析被测离子；离子阱质谱是通过不同离子在离子阱中束缚条件不同来区分离子的质量；飞行时间质谱是通过在给予相同的能量后，质量大的离子飞行速度慢、质量小的离子飞行快这一特点来测定离子的质量。Mass spectrometry is an analytical method for measuring the charge-to-mass ratio of ions. Its principle is to ionize the components in the sample in the ion source to generate positively charged ions with different charge-to-mass ratios. The ion beam, enters the mass analyzer. In the mass analyzer, the electric and magnetic fields are used to make the opposite velocity dispersion occur, and they are respectively focused to obtain a mass spectrum, thereby determining its mass. The commonly used mass spectrometry techniques include quadrupole mass spectrometry, ion trap mass spectrometry, time-of-flight mass spectrometry and so on. Among them, quadrupole mass spectrometry is to analyze the measured ions by using the different trajectories of ions of different masses in the radio frequency field; ion trap mass spectrometry is to distinguish the mass of ions by different ion binding conditions in the ion trap; time-of-flight mass spectrometry is The mass of ions is determined by the characteristics that ions with large mass fly slowly and ions with small mass fly fast after the same energy is given.
目前对于热解产物的研究多是采用先收集热解产物，经离子源电离后再利用质谱分析，这种先收集后检测的方法可能会因为检测前组分间的反应，而无法得到热解过程中热解产物变化规律的真实信息。也有的研究将热解炉通过导管与质谱直接相连，但在热解过程中产生的自由基或反应中间体极不稳定，降低了分析的实时性。同时一些特定分子的离子也是不稳定的，在离子传输过程中也容易发生淬灭，影响检测的完整性。At present, most of the research on pyrolysis products is to collect the pyrolysis products first, and then use mass spectrometry to analyze them after being ionized by the ion source. The real information of the change law of pyrolysis products in the process. In some studies, the pyrolysis furnace is directly connected to the mass spectrometer through a tube, but the free radicals or reaction intermediates generated during the pyrolysis process are extremely unstable, which reduces the real-time performance of the analysis. At the same time, the ions of some specific molecules are also unstable, and are prone to quenching during the ion transmission process, which affects the integrity of the detection.
发明内容Contents of the invention
为了克服现有技术存在的缺陷，本发明的目的是提供一种适合质谱分析的低压高温热解炉及其应用，用于检测样品在热解过程中产生的自由基和中间体。其设计思想是将热解炉直接固定于质谱电离室的前端，通过控制热解炉温度，使样品在不同温度下热解，由于电离室处于真空状态，而热解炉内为低压，因此热解产物会因为压力作用向电解室扩散，使煤热解产物第一时间进入电解室被电离，减少离子损失。In order to overcome the defects in the prior art, the object of the present invention is to provide a low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis and its application for detecting free radicals and intermediates generated during the pyrolysis process of samples. The design idea is to directly fix the pyrolysis furnace on the front end of the mass spectrometry ionization chamber, and control the temperature of the pyrolysis furnace to pyrolyze the samples at different temperatures. Since the ionization chamber is in a vacuum state and the pyrolysis furnace is at low pressure, the thermal The decomposition product will diffuse to the electrolysis chamber due to the pressure, so that the coal pyrolysis product enters the electrolysis chamber and is ionized at the first time, reducing ion loss.
本发明提供了一种适合质谱分析的低压高温热解炉，该热解炉包括炉体、支架、热解室、进样管和差分孔；所述热解炉通过热解室直接与质谱电解室相连；当样品在热解炉中热解时，通过调节炉内的温度使样品在不同温度下发生热解，热解产物由于压力作用向质谱电解室扩散，当经过差分孔后形成分子束进入质谱电解室。The invention provides a low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis. The pyrolysis furnace includes a furnace body, a support, a pyrolysis chamber, a sampling tube and a differential hole; The chambers are connected; when the sample is pyrolyzed in the pyrolysis furnace, the sample is pyrolyzed at different temperatures by adjusting the temperature in the furnace, and the pyrolysis product diffuses to the mass spectrometer electrolysis chamber due to the pressure, and forms a molecular beam after passing through the differential hole. Enter the mass spectrometer electrolysis chamber.
本发明提供的适合质谱分析的低压高温热解炉，所述进样管为99型钢玉管，外径为4mm，内径为2mm。所述差分孔的孔径为0.5mm，材料为铜。In the low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis provided by the present invention, the sampling tube is a 99-type corundum tube with an outer diameter of 4mm and an inner diameter of 2mm. The diameter of the differential hole is 0.5mm, and the material is copper.
本发明提供的适合质谱分析的低压高温热解炉，所述热解炉的温度和压强由热解室控制；热解室控制温度为1200℃；热解室通过分子泵控制压强为1~300Pa。The low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis provided by the present invention, the temperature and pressure of the pyrolysis furnace are controlled by the pyrolysis chamber; the temperature of the pyrolysis chamber is controlled at 1200°C; the pressure of the pyrolysis chamber is controlled by a molecular pump to 1~300Pa .
本发明还提供了所述适合质谱分析的低压高温热解炉的应用，该热解炉应用于固、液、气三相样品热解；其中，气体样品采用质量流量计进样，固体样品采用直接加样，液体样品采用鼓泡进样方式。The present invention also provides the application of the low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis. The pyrolysis furnace is applied to the pyrolysis of solid, liquid and gas three-phase samples; wherein, the gas sample is injected by a mass flow meter, and the solid sample is fed by a The sample is added directly, and the liquid sample is injected by bubbling.
本发明的有益效果是：本发明利用热解炉直接与质谱电离室相连，使热解产物第一时间进入电解室电离，减少样品热解产生的自由基及中间产物的损失。The beneficial effects of the present invention are: the present invention utilizes the pyrolysis furnace to be directly connected with the mass spectrometer ionization chamber, so that the pyrolysis product enters the electrolysis chamber for ionization at the first time, and reduces the loss of free radicals and intermediate products produced by sample pyrolysis.
附图说明Description of drawings
图1是本发明一种适合质谱分析的低压高温热解炉的结构示意图；其中（1）为炉体，（2）为支架，（3）为热解室，（4）为进样管，（5）为差分孔；Fig. 1 is a schematic structural view of a low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis of the present invention; wherein (1) is a furnace body, (2) is a support, (3) is a pyrolysis chamber, and (4) is a sampling tube, (5) is a differential hole;
图2是以飞行时间质谱为例，低压高温热解炉与飞行时间质谱连接示意图；其中（6）为低压高温热解炉，（7）为飞行时间质谱；Figure 2 takes time-of-flight mass spectrometry as an example, a schematic diagram of the connection between a low-pressure high-temperature pyrolysis furnace and a time-of-flight mass spectrometer; (6) is a low-pressure high-temperature pyrolysis furnace, and (7) is a time-of-flight mass spectrometer;
图3是煤炭模型化合物苯甲醚的随温度升高的热解质谱图。Fig. 3 is the pyrolysis mass spectrum of the coal model compound anisole with increasing temperature.
具体实施方式Detailed ways
下面结合附图对本发明做进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings.
如图1所示，本发明一种适合质谱分析的低压高温热解炉，包括炉体、支架、热解室、进样管和差分孔。当样品在热解炉中热解时，通过调节炉内的温度使样品在不同温度下发生热解，热解产物由于压力作用向电解室扩散，当经过差分孔后形成分子束进入飞行时间质谱电解室。As shown in FIG. 1 , a low-pressure high-temperature pyrolysis furnace suitable for mass spectrometry analysis of the present invention includes a furnace body, a support, a pyrolysis chamber, a sampling tube and a differential hole. When the sample is pyrolyzed in the pyrolysis furnace, the sample is pyrolyzed at different temperatures by adjusting the temperature in the furnace, and the pyrolysis product diffuses to the electrolysis chamber due to the pressure, and forms a molecular beam after passing through the differential hole and enters the time-of-flight mass spectrometer electrolysis chamber.
图3为煤炭模型化合物苯甲醚的随温度升高的热解质谱图。分别选取了673K、973K、1073K、1173K和1373K五个具有代表性的温度点。可以从谱图上清晰的看出母体离子和碎片离子的变化趋势，从而分析热解过程。Fig. 3 is the pyrolysis mass spectrum of the coal model compound anisole with increasing temperature. Five representative temperature points of 673K, 973K, 1073K, 1173K and 1373K were selected respectively. The change trend of precursor ions and fragment ions can be clearly seen from the spectrum, so as to analyze the pyrolysis process.
本发明可以应用于样品热解产物自由基和中间体的分析，利用热解炉直接与质谱电离室相连，使热解产物第一时间进入电解室电离，减少样品热解产生的自由基及中间产物的损失。The present invention can be applied to the analysis of free radicals and intermediates of sample pyrolysis products. The pyrolysis furnace is directly connected to the mass spectrometer ionization chamber, so that the pyrolysis products enter the electrolysis chamber for ionization at the first time, reducing the free radicals and intermediates generated by the pyrolysis of samples. loss of product.
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Cited By (3)
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| CN104122322A (en) * | 2014-07-15 | 2014-10-29 | 江西中烟工业有限责任公司 | Method and device for detecting whole process of compound cracking |
| CN105784917A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Application of mass spectrometer to detection process of ionized intermediates in catalytic reaction |
| CN107576717A (en) * | 2017-10-24 | 2018-01-12 | 中国科学技术大学 | A kind of in-situ detector for different diffusion length catalytic reaction gas phase intermediate products |
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