WO2018050090A1 - 微波等离子体炬质谱分析装置及分析方法 - Google Patents

微波等离子体炬质谱分析装置及分析方法 Download PDF

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WO2018050090A1
WO2018050090A1 PCT/CN2017/101736 CN2017101736W WO2018050090A1 WO 2018050090 A1 WO2018050090 A1 WO 2018050090A1 CN 2017101736 W CN2017101736 W CN 2017101736W WO 2018050090 A1 WO2018050090 A1 WO 2018050090A1
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torch
sample
gas
microwave plasma
plasma torch
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PCT/CN2017/101736
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English (en)
French (fr)
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陈焕文
杨美玲
王新晨
屈颖
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东华理工大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber

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  • the invention relates to the field of analytical chemistry, in particular to an analysis device and an analysis method for directly detecting organic components in various morphological samples by using a microwave plasma torch and a mass spectrometer, in particular, the organic components contained in the sample are obtained by a thermal desorption method. Desorbed, then ionized by a microwave plasma torch ionization source, and subjected to high-sensitivity rapid and direct detection by a mass spectrometer to obtain information on the species, content and distribution interval of the organic substance in the sample.
  • the above method is necessary for detailed analysis of the content and composition of organic substances in combustible organic rock minerals.
  • a large number of ore or magma samples are to be measured, both samples containing the desired minerals and samples containing the desired minerals.
  • the samples containing the desired minerals can be screened out and only the required samples are analyzed in detail, the overall analysis time can be greatly reduced and the analysis cost can be reduced. Therefore, there is a need for a fast and reliable method of screening for ore or magma samples.
  • core fluorescence detection is a simple and intuitive method to find the oil and gas interval, under the ultraviolet light, not only the oil core has fluorescence, but also contains a certain mineral composition.
  • the oil-free core can also emit fluorescence similar to oil and gas, which creates the possibility of misjudgment.
  • Mass spectrometry has developed rapidly in recent years, and it has the advantages of fast detection speed, low sample consumption, and fast analysis speed.
  • DESI electrospray desorption ionization
  • the Microwave Plasma Torch (MPT) was first proposed by Professor Jin Qinhan in 1985, and was subsequently improved by Professor Jin and GMHieftje of Indiana University.
  • MPT torch and ICP have a three-tube coaxial structure, but the difference is mainly that the energy of MPT is provided by microwave.
  • MPT Similar to conventional microwave plasma (MWP), MPT easily forms a plasma of Ar, N 2 or even air under normal pressure. Since MPT can generate a stable plasma, and the plasma has a strong ionization capability, MPT no longer appears in the field of analytical chemistry only as a light source, but has been developed as an ionization source for mass spectrometry; currently, MPT has been successfully used. Research in the fields of biological samples, aromatics and pharmaceuticals can be used as ionization sources for the detection of samples in solid, liquid and gaseous forms. Li et al. (Li Y, Yang M, Sun R, et al.
  • the present invention provides a microwave plasma torch mass spectrometer analysis apparatus and an analysis method.
  • the microwave plasma torch mass spectrometer device specifically comprises a sample introduction device working in an atmospheric pressure environment, a microwave plasma torch, a microwave source and a mass spectrometer.
  • the microwave plasma torch is both an ionization source and a desorption device.
  • the sample end of the sample introduction device, the microwave plasma torch flame and the mass spectrometer inlet are distributed at a certain distance and in the same vertical plane, and the microwave plasma torch
  • the open end of the tube head points downward at an angle ⁇ to the sample end, the torch flame and the sample end are at a height d 1 , and the horizontal distance from the mass spectrometer inlet is d 2 .
  • the sample is a solid or a liquid
  • the sample introduction device comprises a horizontally placed sample tray and an aluminum foil coated on the sample tray, the sample is placed on the aluminum foil; the mass spectrometer inlet is on the same level as the sample tray, and the microwave
  • the angle between the axial direction of the plasma torch tube and the horizontally placed sample tray is 30°-60°, d 1 ⁇ 5 mm, and d 2 is about 8-12 mm.
  • the sample tray is a flat plate or a watch glass; when the sample is a liquid, the sample tray is a watch glass. or,
  • the sample is in a gaseous state
  • the sample introduction device is a gas pipe
  • the inlet of the gas pipe is connected to the gas sample to be tested
  • the gas sample outlet is located at the d 1 position below the microwave plasma torch torch, d 1 ⁇ 5 mm
  • the gas sample The axial angle between the outlet axis and the microwave plasma torch tube is 45°-120°, and d 2 is about 5-10 mm.
  • the microwave plasma torch comprises a coaxially assembled inner tube, a middle tube and an outer tube forming a cavity portion, the open end of the cavity portion is provided with a torch, and the tail portion is provided with a tuning. piston.
  • the carrier is introduced into the inner tube, and the auxiliary gas (also called working gas) is introduced into the middle tube.
  • the carrier gas and the auxiliary gas are neutral gases, including inert gas such as argon gas or helium gas or nitrogen gas, and the neutral gas is in the cavity. A portion of the open end is excited to form a plasma.
  • a microwave coupling opening is defined in the outer tube wall, and the coupling ring is fixed on the outer wall of the middle tube at the microwave coupling opening, and the coupling antenna is connected to the coupling ring through the microwave coupling opening, and the coupling antenna is connected with the microwave transmission line outside the device, and the microwave is connected
  • the coupling is transmitted between the outer tube and the middle tube to form a microwave cavity between the outer tube and the middle tube.
  • the tuning piston is a hollow type of "work" type, wherein the empty section is sleeved on the outer wall of the middle tube of the tail of the torch, and the bottom part of the I-shaped part is the inner end surface as the microwave reflection surface, and is located at the inner end of the outer tube of the torch tube, the upper part of the upper part of the torch.
  • the outer end surface is used as the operation surface, and is located outside the tail of the outer tube of the torch; by pushing the outer end surface, the whole of the tuning piston can slide along the axial direction of the middle tube, and the sliding distance of the outer end of the outer tube is limited.
  • the invention further provides a microwave plasma torch mass spectrometry method for detecting organic components in solid, liquid, gas samples or smoke (mixture of solid small particles, small droplets), comprising: installing in an atmospheric pressure environment as described above
  • the microwave plasma torch mass spectrometer analyzes the neutral gas into the inner tube and the middle tube of the microwave plasma, couples the microwave into the microwave plasma torch through the coupling antenna, and uses a wire at the open end of the torch Burning the torch; adjusting the positions of d 1 and d 2 , introducing the sample to be tested, maintaining the ablation time of the torch, decomposing and ionizing the organic component to be tested in the sample, simultaneously starting the mass spectrometer, obtaining the mass spectrometry data of the organic component and completing the sample Mass Spectrometry.
  • the microwave plasma torch and the ion transport tube inlet of the mass spectrometer are placed in the same vertical plane, and the open end of the torch head faces downward at an angle of 30° to 60° with the horizontal plane (preferably 30). ° ⁇ 45°), fine-tune the height (d 1 ) between the open end of the microwave plasma torch and the sample tray on the horizontal stage, and the distance from the mass spectrometer inlet (d 2 );
  • the carrier gas and the auxiliary gas are respectively introduced into the inner tube and the middle tube, and the gas flow rate of the carrier gas 11 is controlled to be 800 to 1200 mL/min (or 800 to 1000 mL/min), and the gas flow rate for controlling the auxiliary gas is 200 to 400 mL/ Min;
  • the detection of gaseous samples includes the following processes:
  • the detection process for smoke includes:
  • the carrier gas and the auxiliary gas are both neutral gases, and the neutral gas is an inert gas or nitrogen.
  • the invention further provides a method of distinguishing between oil-bearing ore and non-oil-bearing ore, comprising the steps of:
  • the blind sample located in the oil-bearing ore area in the PCA three-dimensional score map is determined as the oil-bearing ore, and the blind sample located in the non-oil-bearing ore area is determined as the non-oil-bearing ore.
  • the invention also provides a rapid screening and screening method for combustible organic rock minerals, wherein the core sample is a combustible organic rock, including rocks, ores such as coal, petroleum, natural gas, etc., and the screening method firstly distinguishes the oil-bearing ore by the foregoing method. Non-oily ore is then screened out of the sample judged to be "non-oily ore".
  • the invention combines a microwave plasma torch with a mass spectrometer for mass spectrometry, which can not only detect gas samples, but also perform high-sensitivity rapid and direct detection of solid and liquid samples without sample pretreatment.
  • the desorption and ionization of the component to be tested is completed by means of a microwave plasma torch
  • the ionization efficiency is high, the analysis sample consumption is small, and it is suitable for high cost or rare samples, the analysis speed is fast (the detection process only takes 10s), and the analysis cost is significantly reduced.
  • the invention can analyze the organic components in samples such as ore, natural gas, petroleum, coal, etc., and can monitor the quality of combustible organic resources (oil, coal, natural gas), and can also be applied to the survey of combustible organic rock minerals such as coal, oil and natural gas. And screening, providing technical support for energy exploration, mining and development, and even for the rapid detection of organic components in smoke and exhalation, and applied in the field of safety protection.
  • Figure 1 is a block diagram of the apparatus for analyzing solid and liquid samples of the present invention
  • Example 2 is a first-order mass spectrum obtained by analyzing an organic component in an oil-bearing ore sample in Example 1 of the present invention
  • Example 3 is a first-order mass spectrum obtained by analyzing a non-oil-containing ore sample in Example 2 of the present invention
  • PCA principal component analysis
  • Figure 5 is a structural diagram of a device for analyzing a gas sample according to the present invention.
  • Figure 6 is a first-order mass spectrum of a liquid sample acetaminophen drop in Example 3 of the present invention.
  • Figure 7 is a first-order mass spectrum of nicotine in a smoke sample according to Example 5 of the present invention.
  • Fig. 8 is a first-order mass spectrum of alcohol (ethanol) in exhaled gas in Example 6 of the present invention.
  • sample introduction device 21: sample tray, 22: aluminum foil paper, 23: sample (solid or liquid), 24: generated ions; 25: gas pipe; 26: gas sample outlet;
  • the invention relates to the analysis of organic components in solid, liquid and gaseous samples, and can be applied to the analysis of organic components in various samples such as petroleum, coal, natural gas and the like, combustible organic rock minerals, petroleum, natural gas, liquid medicine, smoke or exhalation. .
  • the present invention uses MPT-MS technology and includes three processes:
  • Ionization ionizing each component molecule into ion ions of each component through an ionization source
  • Mass spectrometry the ion of each component after ionization is detected by a mass spectrometer to obtain organic Information such as species type, content and distribution interval.
  • desorption and ionization are performed by using a microwave plasma torch (MPT) in conjunction with a sample introduction device to operate in an atmospheric pressure environment (which can be completed in a normal pressure open space without a high pressure closed space), and the mass spectrometry uses an existing one.
  • MPT microwave plasma torch
  • MS Mass Spectrometer
  • the temperature of microwave plasma is as high as 2000K.
  • the temperature is favorable for the desorption of the components to be tested; the high-energy particles, especially the high-speed electrons, are generated in the microwave plasma. These particles are in a higher energy state and can interact with the component to be tested when in contact with the sample, and in the state of energy collision, The molecules of the constituents are favorable for desorption and ionization.
  • the samples to be analyzed in the present invention are divided into solid samples such as ore and coal, liquid samples such as petroleum and liquid chemicals, gas samples such as natural gas and exhaled gas, and solid-liquid mixed samples such as pulp and smoke.
  • the invention shows that the MPT-MS can not only analyze the liquid sample and the gaseous sample, but also can directly analyze the solid sample without any pretreatment in the atmospheric pressure environment, and obtain rich material composition information. Therefore, microwave plasma torch mass spectrometry technology has broad prospects in the development and detection of coal, petroleum, natural gas and other minerals.
  • the sample introduction device 2 includes a sample tray 21 and an aluminum foil 22 covering the sample tray 21, the sample tray 21 is placed on a horizontal stage, and the sample 23 is placed on the aluminum foil 22.
  • the sample tray 21 can be a flat plate or a watch glass, and a solid sample is placed on the aluminum foil paper 22;
  • the sample tray 21 is preferably a watch glass, which can be attached to the aluminum foil paper 22 by a pipetting gun. An appropriate amount of the sample solution is dropped into the groove of the surface dish.
  • the sample 23 was thermally desorbed and ionized by a torch of the microwave plasma torch 1 located above the side of the sample introduction device 2, and the organic matter in the sample 23 was decomposed and extracted and ionized into ions of respective organic components.
  • the invention adopts the sample introduction device to realize the external ablation injection of the liquid sample for the first time.
  • the microwave plasma torch MPT can be used as a thermal desorption and ionization source, and an existing microwave plasma torch (such as a microwave plasma torch developed by Changchun Jida & Little Swan Instrument Co., Ltd.) can be used; the present invention provides the following structure Microwave plasma torch.
  • the main body of the microwave plasma torch 1 is a torch tube, and the inner tube 14, the middle tube 15 and the outer tube 16 which are coaxially assembled constitute a cavity portion thereof.
  • the open end of the cavity portion is a head portion, and the tuning piston is provided at the tail portion. 13; a carrier gas 11 is introduced into the inner tube 14, and an auxiliary gas 12 (also called a working gas) is introduced into the middle tube 15, and the carrier gas and the auxiliary gas are neutral gases, including an inert gas such as argon gas or helium gas or nitrogen gas.
  • the neutral gas that is introduced is located inside the inner tube 14, between the middle tube 15 and the inner tube 14, and the neutral gas is excited at the open end of the cavity portion. Plasma is applied to the external sample of the torch.
  • a microwave coupling opening 161 is defined in the wall of the outer tube 16 .
  • the coupling ring 18 is fixed on the outer wall of the middle tube 15 at the microwave coupling opening.
  • the coupling antenna 17 is connected to the coupling ring 18 through the microwave coupling opening 161 . After the coupling antenna 17 is connected to the microwave transmission line and the microwave is introduced (the microwave source power is adjustable within 0 to 200 W), the microwave coupling is transmitted between the outer tube 16 and the middle tube 15 to form a microwave between the outer tube 16 and the middle tube 15. Resonant cavity.
  • the tuning piston 13 is a "work" type hollow kit, wherein the empty section is sleeved on the outer wall of the middle tube 15 at the tail of the torch, and the bottom of the "work” is defined as the inner end surface 131, which is located at the inner end of the outer tube 16 of the torch.
  • the upper part of the word is defined as the outer end surface 132, which is located outside the tail of the outer tube 16 of the torch.
  • the inner end surface 131 between the outer tube 16 and the middle tube 15 serves as a microwave reflecting surface, and the position of the reflecting surface is adjusted by adjusting the position where the piston 13 slides, thereby changing the microwave between the outer tube 16 and the middle tube 15 The transmission distance in .
  • the microwave When the distance between the torch port (head) and the inner end surface 131 of the tuning piston 13 satisfies certain conditions, the microwave will form a standing wave in the torch cavity and also form a stable electromagnetic field structure.
  • the distance between the torch port and the inner end 131 of the tuning piston 13 is an odd multiple of ⁇ /4, and the electric field is always maximum ( ⁇ is the microwave wavelength), and the magnetic field is always zero; if the MPT port (head) is formed and maintained stable
  • the plasma must ensure that the electric field at this point (the torch port) is always the strongest.
  • the inner tube 14 and the middle tube 15 are electrically connected by a conductive rod (wire) for short discharge, and the MPT can be easily ignited (the ignition process provides a process of breaking the minimum electron density of the working gas), so that The torch port (head) forms a stable plasma.
  • the transmission distance of the microwave in the chamber between the outer tube 16 and the middle tube 15 can be changed, thereby changing the electromagnetic field distribution in the microwave cavity between the outer tube 16 and the middle tube 15, thereby changing the electric field of the open end of the cavity portion.
  • the purpose of the magnetic field strength is therefore to adjust the morphology of the plasma torch to produce a stable plasma torch 19, thereby producing a better effect on sample desorption and ionization.
  • the installation of the instrument is as shown in FIG. 1 , wherein the sample tray 21 of the sample introduction device 2 is horizontally placed.
  • the microwave plasma torch 1 and the mass spectrometer inlet 3 are placed on both sides of the sample tray 21 and the three are aligned on the same plane.
  • the open end of the torch head is facing downward and the angle between the axial direction of the torch and the horizontal plane is 30.
  • the mass spectrometer inlet 3 and the sample tray 21 are at the same horizontal plane (the angle between the nozzle and the axial direction of the torch is 120°-150°), and the flame end of the torch 19 generated at the open end of the torch is slightly higher than the sample tray. 21, the height d 1 ⁇ 5 mm from the plane of the sample tray 21, and the horizontal distance d 2 from the mass spectrometer inlet 3 is about 8-12 mm.
  • the length of the torch 19 generated at the open end of the torch is related to the electric field and magnetic field strength of the microwave plasma torch 1, and is also related to the microwave power, the carrier gas, and the working gas flow rate.
  • a carrier gas 11 is introduced into the inner tube 14
  • an auxiliary gas 12 is introduced into the middle tube 15
  • a coupling antenna 17 is connected to the microwave power source, and a microwave is introduced, and the inner end surface 131 of the tuning piston 13 is adjusted by the outer end surface 132.
  • the electric field strength of the open end of the cavity portion is the strongest and the magnetic field strength is the weakest.
  • the ignition of the wire at the open end can generate and form a stable plasma torch 19; moving the sample disk 21
  • the loading platform and the mass spectrometer inlet 3 are such that d 1 is about 3-5 mm and d 2 is about 8-12 mm; an appropriate amount of solid sample is added to the sample pan 21, or to the sample pan 21 by a pipetting gun (at this time) A suitable amount of the solution sample was dropped into the groove of the watch glass, and the torch was held for 10 seconds.
  • the organic component of the sample was desorbed by the torch 19 of the microwave plasma torch 1 and ionized to form charged particles 24, and the mass spectrometer inlet 3 was used as The ion transport nozzles introduce charged particles 24, and the mass spectrometer performs mass spectrometry on the charged particles 24.
  • This analysis is referred to in the present invention as "microwave plasma torch external ablation injection mass spectrometry”.
  • Example 1 Direct mass spectrometry analysis of organic components in ore
  • the organic components in the ore samples were detected by the external ablation injection mass spectrometry of the microwave plasma torch described above.
  • the analysis process refers to the above description and includes the following operations:
  • the carrier gas 11 and the auxiliary gas 12 are respectively introduced into the inner tube 14 and the middle tube 15, and the gas flow rate of the carrier gas 11 is controlled to be 800 to 1000 mL/min, or to 1200 mL/min, and the gas flow rate of the auxiliary gas 12 is controlled to be 200. ⁇ 400mL/min;
  • the microwave is coupled into the microwave plasma 1 torch through the coupling antenna 17, adjusting the tuning piston 13 so that the open end of the torch can be ignited with a wire to produce a stable plasma torch 19; (4) adjust the position of the torch 1, so that the torch tip 19 of the torch 21 to produce a high D about 3mm from the sample tray, away from the mass spectrometer inlet d 2 of about 12mm;
  • the mass spectrometry spectrum of the organic matter in the core sample is shown in Fig. 2.
  • a higher abundance of m/z 127, 155, 281, 295, 309 plasma peaks was observed in the first-order mass spectrum of the core sample. It can be seen from the analysis that the molecular weights corresponding to these higher abundance ion peaks are consistent with the molecular weight of the monoolefin C n H 2n (n ⁇ 7 ).
  • ion peaks of abundant alkane species can be observed in the first-order mass spectrum, which is substantially the same as the known organic components in petroleum.
  • the ions m/z 127, 141, 155 and the like are 1-decene (MW 126), 1-decene (MW 140), 1-undecene (MW 154), etc.
  • the main components in petroleum are saturated hydrocarbons such as alkanes and cycloalkanes, and aromatic hydrocarbons. Therefore, the olefin ion peak observed in the first-order mass spectrum of the core sample may be an alkane in the oil-bearing ore at MPT.
  • the product under the action of MS which is not an organic component contained in the oil-bearing ore itself, but can be used to indicate whether it is an oil-bearing ore.
  • the types and abundances of the ion peaks of the monoolefin species obtained by the MPT-MS for detecting the core samples in this example are shown in Table 1.
  • the core sample can be quickly determined to be an oil-bearing ore by means of a standard mass spectrum of organic matter.
  • Table 1 Species and abundances of ion peaks of monoolefins obtained by detecting core samples
  • the present embodiment shows that the mass spectrometry analysis result of the external ablation injection of the microwave plasma torch of the present invention is accurate, and the plasma torch desorption ionization process only takes several seconds.
  • the mass spectrometry result can be given in one minute, and the ore can be realized.
  • the rapid and accurate analysis of the organic components contained, and in turn, can determine which combustible organic rock ore, for example, the oil-bearing ore is judged in this example.
  • Example 2 Differentiating oil-bearing ore and non-oil-bearing ores and screening for combustible organic rock minerals
  • PCA Principal Component Analysis
  • the core sample is a non-oily ore.
  • the mass spectrometry data of oil-bearing ore was taken as the first group
  • the mass spectrometry data of non-oil-bearing ore was taken as the second group
  • the two sets of data were imported into MATLAB software for principal component analysis, and the three-dimensional discrimination result shown in Fig. 4 was obtained, and the three-dimensional score in PCA was obtained.
  • PC1, PC2, and PC3 are the contribution rates of the variances in each direction. The larger the percentage of contribution rate, the more obvious the differentiation effect.
  • Figure 4 can be used as a distinguishing model between oil-bearing ore and oil-free ore. It shows that the microwave plasma torch mass spectrometry combined with principal component analysis can quickly distinguish between oil-bearing ore-free and oil-free ore samples.
  • the distinguishing model of Figure 4 can be applied to distinguish between oil-bearing ore and non-oil-bearing ore in a blind sample: separately detect and collect the respective mass spectrometry data for large-volume core samples, and mark them as the third group of “blind samples”.
  • a set of "oil-bearing ore” mass spectrometry data, a second set of "non-oil-bearing ore” mass spectrometry data, three sets of data were imported into MATLAB software for principal component analysis, and the third group of blind samples were observed in the PCA three-dimensional map (differentiation In the model, if a blind spot falls in the oil-bearing ore area, it is determined to be an oil-bearing ore; if the falling point is in the non-oil-bearing ore area, it is determined to be a non-oil-bearing ore.
  • the oil-bearing ore can be quickly and reliably distinguished from the non-oil-bearing ore, thereby screening out the oil-free ore, avoiding unnecessary and time-consuming further analysis; on the other hand, combining the core samples in the formation
  • the location can determine the distribution of oil-bearing ore in the formation and help find oil exploration.
  • the core sample of the embodiment may also be a rock ore such as coal or natural gas, and details are not described herein again. It will be understood that for other types of combustible organic rock, “oil-bearing ore” and “non-oil-containing ore” are only used as a distinguishing mark, and the concept of "oil” should be understood as a broader “organic matter”. It can be seen that the method of the present embodiment can be applied to the general survey and screening of combustible organic rock minerals such as coal, petroleum, natural gas, etc., and provides technical support for energy exploration, mining and development.
  • Example 3 Direct mass spectrometry analysis of organic matter in petroleum
  • the organic matter in the liquid sample was subjected to mass spectrometry using the microwave ablation external ablation injection described above.
  • Sample petroleum sample, liquid.
  • the analysis includes the following steps:
  • the microwave plasma torch 1 and the ion transport tube inlet 3 of a mass spectrometer are placed in the same vertical plane, and the open end of the torch head faces downward at an angle of 30° to the water surface ( ⁇ ), fine-tuning a height d 1 between the open end of the microwave plasma 1 torch and the sample tray (surface dish) 21 on the horizontal stage, and a distance d 2 from the mass spectrometer inlet;
  • the carrier gas 11 and the auxiliary gas 12 are respectively introduced into the inner tube 14 and the middle tube 15, and the gas flow rate of the carrier gas 11 is controlled to be 800 to 1000 mL/min, or to 1200 mL/min, and the gas flow rate of the auxiliary gas 12 is controlled to be 200. ⁇ 400mL/min;
  • composition of the present example obtained the composition and distribution of the organic components in the petroleum sample, and the organic components such as oil-containing alkanes were detectable and presumed to be substantially the same as the known organic components of the petroleum sample.
  • microwave plasma torch external ablation injection can also directly analyze the active components in the liquid sample acetaminophen drops, and the operation process is similar, and the analysis results are shown in FIG. 6 .
  • the present invention proposes an external ablation injection of a microwave plasma torch for mass spectrometry analysis of a liquid sample, the result is accurate, and the analysis process is simple and rapid.
  • This embodiment shows that the invention can realize rapid and accurate determination of organic substances in liquid samples, and can be applied to product quality control detection of petroleum, medicine and the like.
  • the sampling device 52 is a gas pipeline 25, the inlet pipeline 25 is connected to the test gas sample, the gas sample outlet 26 is positioned below the microwave plasma torch 1 d 1 of the torch 19 and the position of the pipeline axis 25
  • the axial angle ⁇ of the torch 19 is 60°-120°
  • the gas sample of the gas sample outlet 26 of the gas pipe is thermally desorbed and ionized by the torch of the microwave plasma torch 1 to decompose the organic matter in the gas sample. It exits and ionizes the ions of each organic component and enters the mass spectrometer through a horizontally placed mass spectrometer inlet 3 (150° axial to the torch).
  • Example 4 Direct mass spectrometry analysis of organic components in natural gas
  • the organic components in the gas sample were subjected to mass spectrometry using the microwave plasma torch mass spectrometer described above (using the sample introduction device shown in Fig. 5).
  • the analysis includes the following steps:
  • the microwave plasma torch 1, the gas pipe gas sample outlet 26 and the ion transport tube inlet 3 of a mass spectrometer are placed in the same vertical plane, the gas pipe gas sample outlet 26 faces upward, and the torch head opening The end is downward and at an angle ( ⁇ ) of 60° to the gas sample outlet 26 of the gas pipe, fine-tuning the height d 1 between the open end of the microwave plasma torch and the gas sample outlet 26 of the gas pipe, and injecting with the mass spectrometer The distance d 2 of the mouth;
  • the carrier gas 11 and the auxiliary gas 12 are respectively introduced into the inner tube 14 and the middle tube 15, and the gas flow rate of the carrier gas 11 is controlled to be 800 to 1000 mL/min, or to 1200 mL/min, and the gas flow rate of the auxiliary gas 12 is controlled to be 200. ⁇ 400mL/min;
  • composition and distribution of the organic components in the natural gas sample were obtained by analysis.
  • This embodiment shows that the invention can realize rapid and accurate determination of organic substances in gas samples, and can be applied to product quality control detection of natural gas and the like.
  • Example 5 Direct mass spectrometry analysis of nicotine in cigarette smoke
  • Sample Cigarette smoke, a mixture of solid small particles and liquid.
  • the analysis includes the following steps:
  • the carrier gas 11 and the auxiliary gas 12 are respectively introduced into the inner tube 14 and the middle tube 15, the gas flow rate of the carrier gas 11 is controlled to be 800 to 1200 mL/min, and the gas flow rate of the auxiliary gas 12 is controlled to be 200 to 400 mL/min;
  • the microwave is coupled into the microwave plasma 1 torch through the coupling antenna 17, adjusting the tuning piston 13 so that the open end of the torch can be ignited with a wire to produce a stable plasma torch 19;
  • the mass spectrometry spectrum of cigarette smoke is shown in Fig. 7. It can be observed that the intensity of ion m/z 163 is the highest, being 111000 cps.
  • the ion m/z 163 is determined to be a quasi-molecular ion peak of nicotine by means of a standard nicotine mass spectrogram.
  • This embodiment shows that the external ablation sampling mass spectrometry of the microwave plasma torch of the present invention can directly analyze the nicotine in cigarette smoke, and the result is accurate, and the detection process can be completed in one second, which can realize the cigarette smoke. Rapid and accurate identification and analysis of nicotine.
  • Example 6 Direct mass spectrometry analysis of alcohol (ethanol) in exhaled gases
  • the mass spectrometry of alcohol (ethanol) in the exhaled gas was carried out by using the above-described microwave plasma torch mass spectrometer (using the sample introduction device shown in Fig. 5).
  • the analysis includes the following steps:
  • the microwave plasma torch 1, the gas pipe gas sample outlet 26 and the ion transport tube inlet 3 of a mass spectrometer are placed in the same vertical plane, the gas pipe gas sample outlet 26 faces upward, and the torch head opening The end is downward and at an angle ( ⁇ ) of 60° to the gas sample outlet 26 of the gas pipe, fine-tuning the height d 1 between the open end of the microwave plasma torch and the gas sample outlet 26 of the gas pipe, and injecting with the mass spectrometer The distance d 2 of the mouth;
  • the carrier gas 11 and the auxiliary gas 12 are respectively introduced into the inner tube 14 and the middle tube 15, the gas flow rate of the carrier gas 11 is controlled to be 800 to 1200 mL/min, and the gas flow rate of the auxiliary gas 12 is controlled to be 200 to 400 mL/min;
  • This embodiment shows that the external ablation injection mass spectrometry of the microwave plasma torch of the present invention can directly analyze the alcohol (ethanol) in the exhaled gas, and the result (as shown in FIG. 8) is accurate, and can be within one second.
  • the detection process can complete the rapid and accurate identification and analysis of alcohol (ethanol) in the exhaled gas. It is expected to be used in the analysis and testing of whether the driver is driving or not.
  • the method can also be used to detect nicotine in the exhaled gas, organic drugs, etc., and is applied to specific areas such as safety protection and anti-narcotics detection.
  • the mass spectrometric analysis of the organic matter in the sample by the microwave plasma torch 1 and the mass spectrometer 3 can directly desorb, ionize and mass spectrometry the solid, liquid and gas samples without analyzing the sample, and analyze the speed. fast.
  • the speed of ionization analysis is related to the gas flow rate and microwave source power in the microwave plasma torch.
  • the magnitude of the carrier gas and auxiliary gas flow rate affects the size and stability of the torch.
  • a stable torch is obtained by adjusting the carrier gas input and the flow rate of the working gas input.
  • the carrier gas flow has a large impact on the signal strength.
  • the carrier gas flow rate is too small, the rate at which the formed plasma desorbs and ionizes the sample and enters the mass spectrum is correspondingly slowed down.
  • the carrier gas flow rate is too large, the formed plasma is easily blown and splattered by the airflow after the sample is applied, and the detection result is not good.
  • the flow rate of the carrier gas selected in the present invention is 800 to 1200 mL/min.
  • work gas sisted The gas flow rate also has an influence on the detection result.
  • the working gas flow rate is small, the volume of the plasma is small, the sample and the plasma are insufficiently applied, and the signal intensity is small; when the working gas flow rate is too large, the plasma is cooled on the one hand to make the temperature The reduction is not conducive to sample excitation, and on the other hand a part of the energy of the plasma will be consumed on the excited argon atoms to make the signal intensity smaller.
  • the working gas flow rate of the invention is selected to be 200-400 mL/min.
  • the power of the microwave source is adjustable from 0 to 200 W. Under the condition of high microwave source power, the generated torch is too high in temperature, so that most of the sample is ablated and decomposed, desorbed and ionized to obtain the relative abundance of the ion peak of the component to be tested. Lower, weaker.
  • the power determined by the present invention is 30 to 50 W.
  • the open end of the microwave plasma torch is ignited by a neutral gas of the outlet of the wire to generate a torch.
  • the torch is a plasma stream, which interacts with the sample to desorb and ionize the organic matter in the sample into a charged particle stream, and is introduced into the mass spectrometer to start recording data. The entire analysis process takes about 10 seconds.
  • the ionization efficiency is high, the sample consumption is small in the ionization analysis, and the analysis speed is fast, and the analysis cost is significantly reduced for high cost or rare samples.
  • the microwave plasma torch mass spectrometer device of the invention combines a microwave plasma torch and a mass spectrometer scanner, and can be manufactured and used.
  • the microwave plasma torch mass spectrometry method can quickly and accurately analyze samples of solid, liquid and gas different states. It can be used for the detection of organic components in coal, oil, natural gas and other minerals to achieve the general survey and screening of combustible organic rock minerals, which can be applied in industry.

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Abstract

一种微波等离子体炬质谱分析装置及分析方法，该装置以微波等离子体炬（1）作为电离源和解吸源，针对固体、液体和气态样品（23）设置对应的进样装置（2），利用微波等离子体炬焰烧蚀将样品（23）中待测有机成分解吸并电离，通过质谱扫描仪获取有机成分质谱检测数据并完成样品质谱分析。该装置及分析方法能直接对矿石、天然气、石油、烟雾、呼气等样品中有机成分进行分析，可应用于可燃有机岩矿产的普查与筛选、含有有机成分各类产品的质量监控。

Description

微波等离子体炬质谱分析装置及分析方法 技术领域
本发明涉及分析化学领域，特别涉及利用微波等离子炬和质谱仪对各种形态样品中有机成分进行直接检测的分析装置及分析方法，具体为通过热解吸方法，使得样品中所含的有机物成分解吸出来，随后通过微波等离子体炬电离源将其电离，并由质谱仪进行高灵敏度的快速直接检测，从而获得该样品中有机物种类、含量及分布区间等信息。
背景技术
在现代能源的供给中，石油、煤、天然气占据了非常大的比重。可燃有机岩矿床(包括三类矿床，固体燃料矿床，如煤、油页岩等；液态燃料矿床，如石油等；气体燃料矿床，如天然气、煤层气等)的勘探与开采很重要，世界上每年开采的矿产，70％来自可燃有机岩矿产。此外，可燃有机岩矿产还是化工和医药产业的重要原料，单从石油中就可提炼出1000多种产品可供使用。
在石油、煤、天然气等矿产资源的勘探开发中，矿石或岩浆样品所含有机物的分析是必不可少的环节。针对有机物成分的分析，目前需要应用许多技术，主要包括：1)分子有机地球化学方法，近几十年来在石油勘探领域取得了巨大成就，该法是以GC、GC/MS、GC/MS/MS为核心发展起来的技术。2)从煤岩学中发展起来的有机矿石学方法，利用光学显微技术研究矿床中的固态分散有机物质。3)其它的物理学和化学方法，包括微量元素分析，C、H、O、N元素分析，以及核磁共振、红外光谱、X-衍射等光谱分析和电子探针、质子探针等微束分析。一些可萃有机物的测定直接用萃取等化学手段进行测量。
上述方法对于详细分析可燃有机岩矿产中有机物质的含量和成分是必要的。然而在勘探过程中，会有大量的矿石或岩浆样品需要测定，里面既有含有所需矿物的样品，也有不含所需矿物的样品。利用上述方法测定单一样品时，需要较长的时间。面对大量样品时，如果能将不含所需矿物的样品筛选出去，只详细分析所需要的样品，即可大大缩短整体分析时间并降低分析成本。因此，需要一种快速可靠的筛选矿石或岩浆样品的分析方法。虽然在石油等矿产的勘探领域，岩芯荧光检测是寻找判定油气层段的一种简便而又直观的方法，但在紫外光的照射下，不仅含油岩芯具有荧光，而且含有某种矿物成分的不含油岩芯亦可发出与油气相似的荧光，这就造成了误判的可能。
质谱分析技术近年来有了飞速的发展，它有检测速度快，耗样量少、分析速 度快等优点。2004年，Cooks等提出的电喷雾解吸电离(DESI)技术是常压质谱分析研究时代的开端。微波等离子体炬(MPT)是由金钦汉教授于1985年首先提出，随后由金教授和美国印第安纳大学的G.M.Hieftje等共同改进而成。其作为一种激发光源，已广泛运用于原子光谱测量，MPT炬管与电感耦合等离子体(ICP)都具有三管同轴的结构，但不同之处主要在于MPT的能量由微波提供。与传统的微波等离子体(MWP)类似，MPT在常压下易形成Ar、N2甚至空气的等离子体。由于MPT能够产生稳定的等离子体，而等离子体又具有很强的电离能力，MPT已经不再只以光源的角色出现在分析化学领域，继而被开发成为质谱的电离源；目前，MPT已成功用于生物样品、芳烃及药物等领域的研究，能作为电离源用于对固态、液态及气态形式的样品检测中。李等人(Li Y,Yang M,Sun R,et al.Journal of Mass Spectrometry Jms,2016,51(2):159-164.)采用气动雾化进样装置对矿井水样中的铀进行直接质谱分析，检出限达31.03ng·L-1，建立了矿井水样中痕量铀的直接质谱分析方法。然而，这些已有的检测手段均需较为繁琐与复杂的气动雾化进样装置，不利于样品的快速、高通量分析，且存在设备成本较高等不足。因此，使样品引入方式变得简单、便捷、低成本，对于MPT来说具有重要意义。目前，尚没有文献报道微波等离子体炬质谱技术检测煤、石油、天然气等矿产中含有的有机成分。
发明内容
为了解决上述问题，本发明提供一种微波等离子体炬质谱分析装置及分析方法。
本发明提供的微波等离子体炬质谱分析装置，具体包括大气压环境下工作的进样装置、微波等离子体炬、微波源和质谱仪。所述微波等离子体炬既为电离源也为解吸装置，进样装置的样品端、微波等离子体炬炬焰和质谱仪进样口的分布存在一定距离且处于同一垂直平面，微波等离子体炬炬管头部开口端朝下以一夹角α指向样品端，炬焰尾部与样品端高度为d1，与质谱仪进样口的水平距离为d2。
所述样品为固体或液体，所述进样装置包括水平放置的样品盘和包覆该样品盘的铝箔纸，样品置于铝箔纸上；质谱仪进样口与样品盘在同一水平面上，微波等离子体炬炬管轴向与水平放置的样品盘夹角α为30°-60°，d1≤5mm，d2约为8-12mm。所述样品为固体时，所述样品盘为平盘或表面皿；所述样品为液体时，所述样品盘为表面皿。或者，
所述样品为气态，所述进样装置为一输气管，输气管的入口连接待测气体样 品，气样出口位于微波等离子体炬焰炬的下方d1位置，d1≤5mm，且气样出口轴向与微波等离子体炬炬管轴向夹角β为45°-120°，d2约为5-10mm。
以上所述微波等离子体炬质谱分析装置中，所述微波等离子体炬管由同轴装配的内管、中管和外管构成腔体部分，腔体部分开口端产生焰炬，尾部设置有调谐活塞。
内管中通入载体，中管中通入辅助气体(也称工作气)，载气和辅助气体均为中性气体，包括氩气、氦气等惰性气体或氮气，中性气体在腔体部分的开口端被激发形成等离子体。
外管壁上开设有一微波耦合开口，耦合环固定在该微波耦合开口处的中管外壁上，耦合天线穿过该微波耦合开口与耦合环连接，耦合天线与装置外的微波传输线连接，将微波耦合传输至外管和中管之间从而在外管和中管间形成微波谐振腔。
所述调谐活塞为一“工”字型中空的套件，其中空段套于炬管尾部的中管外壁，工字底部为内端面作为微波反射面，位于炬管外管内侧尾部，工字上部为外端面作为操作面，位于炬管外管尾部外侧；借助推动外端面使调谐活塞整体能沿中管轴向滑动，并由外管尾端外壁对滑动距离限位。
本发明进一步提供一种针对固体、液体、气体样品或烟雾(固体小颗粒、小液滴的混合)中有机成分进行检测的微波等离子体炬质谱分析方法，包括：在大气压环境下安装前面所述的微波等离子体炬质谱分析装置，向微波等离子体的内管和中管中通入中性气体，利用耦合天线将微波耦合至微波等离子体炬管内，并在炬管的开口端用金属丝引燃产生焰炬；调整d1和d2位置，引入待测样品，保持焰炬烧蚀时间将样品中待测有机成分解吸并电离，同时启动质谱扫描仪，获取有机成分质谱检测数据并完成样品质谱分析。
其中，针对固体和液体样品的方法被称作外部烧蚀进样电离质谱分析方法。具体的：
针对固体样品检测包括以下过程：
(1)将微波等离子体炬与质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水平面成30°～60°夹角(较好为30°～45°)，微调微波等离子体炬管的开口端与水平承载台上样品盘之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
(2)将载气、辅助气分别通入内管和中管，控制载气11的气体流速为800～1200mL/min(或800～1000mL/min)，控制辅助气的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
(4)调整炬管的位置，使炬管产生的焰炬尖端距样品盘高d1≤5mm(较好约1～3mm)，距质谱仪进样口d2约8～12mm(较好为10mm)；
(5)将固体样品置于包裹有铝箔纸的样品盘上；
(6)启动质谱扫描仪，保持焰炬烧蚀时间约10s，获取检测结果。
针对液体样品检测包括以下过程：
(1)将微波等离子体炬1与一质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水面平成30°～60°夹角(较好为30°)，微调微波等离子体炬管的开口端与表面皿之间的高度d1，以及与质谱仪进样口的距离d2；
(2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min(或800～1000mL/min)，控制辅助气的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
(4)调整炬管的位置，使产生的焰炬尖端距表面皿凹槽高d1≤5mm(较好约3～5mm)，距质谱仪进样口d2约8～12mm(较好为12mm)；
(5)用移液枪将10μL的溶液样品滴入包裹有铝箔纸的表面皿的凹槽里；
(6)启动质谱扫描仪，保持焰炬烧蚀约10s，获取检测结果。
针对气态样品检测包括以下过程：
(1)将微波等离子体炬、输气管气样出口与质谱扫描仪的离子传输管进样口置于同一竖向平面，输气管气样出口朝上，炬管头部开口端朝下且与输气管气样出口夹角β为45°-120°(优选60°)，微调微波等离子体炬管的开口端与质谱仪进样口的距离d2，以及与输气管气样出口之间的高度d1；
(2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min(或800～1000mL/min)，控制辅助气的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
(4)调整炬管的位置，使产生的焰炬尖端距输气管气样出口26的距离d1≤5mm(优选约3mm)，距质谱仪进样口距离d2约为5～10mm(优选8～10mm)；
(5)向输气管中通入气态样品或向输气管中呼气；
(6)启动质谱扫描仪，保持焰炬燃烧约10s，获取检测结果。
针对烟雾的检测过程包括：
(1)将微波等离子体炬与质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水平面成30°夹角(α)，微调微波等离子体炬管的开口端与样品盘之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
(2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min，控制辅助气的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，以使在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
(4)调整炬管的位置，使炬管产生的焰炬尖端距样品盘高d1约15mm，距质谱仪进样口d2约12mm；
(5)将香烟正在燃烧的头部置于包裹有铝箔纸的样品盘上，或直接将香烟正在燃烧的头部置于样品盘所在的位置处代替样品盘，使香烟烟雾自然向上漂浮；
(6)启动质谱扫描仪，保持焰炬烧蚀约10s，获取检测结果。
以上所述的微波等离子体炬质谱分析方法中，所述载气和辅助气均为中性气体，中性气体为惰性气体或氮气。
本发明进一步提供一种区分含油矿石和非含油矿石的方法，包括以下步骤：
1)利用所述微波等离子体炬质谱分析方法对批量岩芯样品分别检测并收集各自质谱检测数据，将一级谱图含有质量相差14(CH2)的离子峰的样品标记为“含油矿石”，将没有这样的离子峰的样品标记为“非含油矿石”；
2)对待检测的大批量岩芯样品分别检测并收集各自质谱检测数据，将其标记为“盲样”，将含油矿石的质谱检测数据、非含油矿石的质谱检测数据、盲样的质谱检测数据共三组数据采用主成分分析法进行分析，得到能区分含油矿石区域和非含油矿石区域的PCA三维得分图；
3)将在PCA三维得分图中落点位于含油矿石区域的盲样判定为含油矿石，将落点位于非含油矿石区域的盲样判定为非含油矿石。
本发明还提供一种对可燃有机岩矿产的快速普查与筛选方法，所述岩芯样品为可燃有机岩，包括煤、石油、天然气等岩石或矿石，该筛选方法首先利用前述方法区分含油矿石和非含油矿石，然后将判定为“非含油矿石”的样品筛除。
本发明将微波等离子体炬配合质谱扫描仪进行质谱分析，不仅能针对气体样品进行检测，还能对固体、液体样品进行高灵敏度的快速直接检测而无需样品预处理。利用本发明的装置和方法，待测成分的解吸和电离利用微波等离子体炬完 成，电离效率高，分析样品消耗量少而适用于高成本或稀有样品，分析速度快(检测过程仅需10s)，分析成本显著降低。本发明能对矿石、天然气、石油、煤等样品中有机成分进行分析，对可燃有机资源(石油、煤、天然气)进行质量监控，还能应用于煤、石油、天然气等可燃有机岩矿产的普查与筛选，为能源勘探、开采和开发提供技术支持，甚至还能对烟雾、呼气中有机成分进行快速检测而应用在安全防护等领域。
附图说明
图1是本发明针对固体、液体样品进行分析的装置构成图；
图2是本发明实施例1中对含油矿石样品中有机成分分析所得一级质谱图；
图3是本发明实施例2中对非含油矿石样品分析所得一级质谱图；
图4为本发明实施例2区分不含油矿石及含油矿石的主成分分析(PCA)结果三维图；
图5为本发明针对气体样品进行分析的装置构成图；
图6为本发明实施例3中液体样品对乙酰氨基酚滴剂的一级质谱图；
图7为本发明实施例5中烟雾样品中尼古丁的一级质谱图；
图8为本发明实施例6中呼出气体中的酒精(乙醇)的一级质谱图。
图中附图标记表示为：
1：微波等离子体炬；11：载气；12：辅助气；13：调谐活塞，132：外端面，131：内端面，14：内管，15：中管，16：外管；161：微波耦合开口；162：(外管尾端)外壁；17：耦合天线，18：耦合环，19：焰炬；
2：进样装置，21：样品盘，22：铝箔纸，23：样品(固体或液体)，24：产生的离子；25：输气管；26：气样出口；
3：质谱仪进样口。
具体实施方式
本发明涉及对固体、液体和气态样品中有机成分的分析，可应用于石油、煤、天然气等可燃有机岩矿产、石油、天然气、药液、烟雾或呼气等各种样品中有机成分的分析。本发明使用MPT-MS技术，包括三方面的过程：
解吸：通过热解吸方法，使得样品中所含的有机成分解吸出来成为各成分分子；
电离：通过电离源将各成分分子电离为各成分离子；
质谱分析：由质谱扫描仪对电离后各成分离子进行检测，获得该样品中有机 物种类、含量及分布区间等信息。
本发明中，解吸和电离是使用微波等离子体炬(MPT)配合进样装置在大气压环境下工作(在常压开放空间即可完成，无需高压密闭空间)共同完成的，质谱分析使用已有的质谱扫描仪(MS)。
通过对MPT的研究，发明人认为虽然MPT解吸电离原理目前还不明确，但微波等离子体的温度和高能粒子对解吸电离过程起着至关重要的促进作用，微波等离子体的温度高达2000K，这个温度有利于待测成分的解吸；微波等离子体中产生高能粒子，尤其是高速电子，这些粒子处于较高能态，在与样品接触时能与待测成分相互作用，在能量碰撞的状态下，待测成分的分子有利于被解吸电离。
本发明中被分析的样品，分为矿石、煤等固体样品，石油、药液等液体样品，天然气、呼气等气体样品，以及矿浆、烟雾等固液混合样品。本发明表明，MPT-MS不仅能够分析液态样品、气态样品，还能在大气压环境下无需任何预处理，对固体样品直接进行分析，得到丰富的物质成分信息。因此，微波等离子体炬质谱技术在煤、石油、天然气等矿产的开发检测中具有广阔前景。
以下围绕上述内容进行详细说明。
对固体、液体样品的分析
如图1所示，进样装置2包括样品盘21和包覆该样品盘21的铝箔纸22，样品盘21放置在一水平方向的承载台上，样品23置于铝箔纸22上。对于固体样品，样品盘21可为平盘或表面皿，取固体样品放在铝箔纸22上；对于液体样品，样品盘21最好为表面皿，可通过移液枪向贴有铝箔纸22的表面皿凹槽处滴入适量的样品溶液。样品23由位于进样装置2侧上方的微波等离子体炬1的焰炬对其进行热解吸和电离，将样品23中的有机物成分解吸出来并电离为各有机成分离子。本发明采用该进样装置首次实现对液体样品外部烧蚀进样。
本发明中，微波等离子体炬MPT作为热解吸和电离源，可使用已有的微波等离子体炬(如长春吉大·小天鹅仪器有限公司研制的微波等离子体炬)；本发明提供以下结构的微波等离子体炬。
参见图1，微波等离子体炬1主体为炬管，由同轴装配的内管14、中管15和外管16构成其腔体部分，腔体部分开口端为头部，尾部设置有调谐活塞13；内管14中通入载气11，中管15中通入辅助气体12(也称工作气体)，载气和辅助气体均为中性气体，包括氩气、氦气等惰性气体或氮气，通入的中性气体分别位于内管14内部、中管15和内管14之间，中性气体在腔体部分的开口端被激发形 成等离子体，使之作用于炬管外部样品。
在图1中，外管16壁上开设有一微波耦合开口161，耦合环18固定在该微波耦合开口处的中管15外壁上，耦合天线17穿过该微波耦合开口161而与耦合环18连接，在耦合天线17连接微波传输线并引入微波(微波源功率在0～200W内可调)后，将微波耦合传输至外管16和中管15之间从而在外管16和中管15间形成微波谐振腔。调谐活塞13为一“工”字型中空的套件，其中空段套于炬管尾部的中管15外壁，“工”字底部定义为内端面131，位于炬管外管16内侧尾部，“工”字上部定义为外端面132，位于炬管外管16尾部外侧，借助推动外端面132使调谐活塞13整体能沿中管15轴向滑动，并由外管16尾端外壁162对滑动距离限位；位于外管16和中管15之间的内端面131作为微波反射面，通过调谐活塞13滑动的位置来调节该反射面的位置，从而改变微波在外管16和中管15之间腔室中的传送距离。
当炬管端口(头部)与调谐活塞13的内端面131之间的距离满足一定条件时，微波将在炬管谐振腔内形成驻波，同时也形成了稳定的电磁场结构。炬管端口距调谐活塞13内端面131的距离为λ/4的奇数倍处的电场恒为最大(λ为微波波长)，磁场恒为零；若要在MPT端口(头部)形成和维持稳定的等离子体，必须保证该处(炬管端口)电场恒为最强。此时，用导体棒(金属丝)将内管14和中管15导通短促放电，MPT可以很容易被点燃(点燃过程即提供击穿工作气体的最小电子密度的过程)，这样就可以在炬管端口(头部)形成稳定的等离子体。
通过调谐活塞13能够改变微波在外管16和中管15之间腔室中的传送距离，进而改变外管16和中管15间微波谐振腔内的电磁场分布，达到改变腔体部分开口端的电场和磁场强度的目的，因此能调整等离子体焰炬的形态而产生稳定的等离子体焰炬19，从而产生对样品解吸和电离的较好效果。
使用该进样装置2、微波等离子体炬1配合质谱扫描仪对固体或液体样品中有机成分进行质谱分析，仪器的安装如图1所示，其中：进样装置2的样品盘21水平放置，微波等离子体炬1和质谱仪进样口3分置在样品盘21两侧且三者在同一平面上对位，炬管头部开口端朝下且炬管轴向与水平面夹角α为30°-60°，质谱仪进样口3与样品盘21在同一水平面(与炬管轴向呈120°-150°夹角)，炬管开口端产生的焰炬19焰尾略高于样品盘21，与样品盘21平面的高度d1≤5mm，与质谱仪进样口3的水平距离d2约为8-12mm。炬管开口端产生的焰炬19长短与微波等离子体炬1的电场和磁场强度有关，另外还与微波功率、载气和工作气流速相关。
安装好仪器后进行如下操作：内管14中通入载气11，中管15中通入辅助气12，耦合天线17连接微波功率源并引入微波，利用外端面132调整调谐活塞13内端面131在炬管轴向的位置，使得腔体部分开口端的电场场强最强而磁场强度最弱，此时利用金属丝在开口端点火能产生并形成稳定的等离子体焰炬19；移动样品盘21的承载台和质谱仪进样口3，使d1约为3-5mm，d2约为8-12mm；向样品盘21中加入适量固体样品，或通过移液枪向样品盘21(此时为表面皿)凹槽里滴入适量的溶液样品，保持焰炬10s，利用微波等离子体炬1的焰炬19对样品中有机成分进行解吸并电离形成带电粒子24，质谱仪进样口3作为离子传输管口引入带电粒子24，质谱仪对带电粒子24进行质谱分析。该分析在本发明中被称作“微波等离子体炬外部烧蚀进样质谱分析”。
以下结合具体实施例详细说明如何利用本发明对固体、液体样品进行微波等离子体炬外部烧蚀进样质谱分析。
实施例1：对矿石中有机成分进行直接质谱分析
采用以上所述微波等离子体炬外部烧蚀进样质谱分析对矿石样品中有机成分进行检测。
样品：岩芯碎粒。
分析过程参照以上描述，包括以下操作：
(1)将微波等离子体炬1与一质谱扫描仪的离子传输管进样口3置于同一竖向平面，且炬管头部开口端朝下与水平面成30°夹角(α)，微调微波等离子体1炬管的开口端与水平承载台上样品盘21之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
(2)将载气11、辅助气12分别通入内管14和中管15，控制载气11的气体流速为800～1000mL/min，或至1200mL/min，控制辅助气12的气体流速为200～400mL/min；
(3)打开一微波功率源，将微波通过耦合天线17耦合至微波等离子体1炬管内，调整调谐活塞13以使在炬管的开口端可用金属丝引燃产生稳定的等离子体焰炬19；(4)调整炬管1的位置，使炬管产生的焰炬19尖端距样品盘21高d1约3mm，距质谱仪进样口d2约12mm；
(5)用镊子将固体样品置于包裹有铝箔纸22的样品盘21上；
(6)保持焰炬19烧蚀时间约10s(利用微波等离子体炬的焰炬对样品进行解吸和电离)，同时启动质谱扫描仪，获取检测结果。
该岩芯样品中有机物的质谱分析谱图如图2所示。在岩芯样品的一级质谱图中可观察到具有较高丰度的m/z 127,155,281,295,309等离子峰。通过分析可知，这些具有较高丰度的离子峰对应的分子量均与单烯烃CnH2n(n≥7)的分子量一致。此外，在一级质谱图中还可观察到丰富的烷烃类物质的离子峰，这与石油中已知有机成分基本相同。借助部分有机物质的标准质谱图，可确定离子m/z 127,141,155等为1-壬烯(MW 126)，1-癸烯(MW 140)，1-十一烯(MW 154)等，查阅资料可知，石油中的主要成分为烷烃、环烷烃等饱和烃类以及芳香烃等，因此，在岩芯样品的一级质谱图中观察到的烯烃类离子峰，其可能为含油矿石中的烷烃在MPT-MS作用下的产物，其虽不是含油矿石本身所含有的有机成分，但却可用以指示是否为含油矿石。本实施例采用MPT-MS检测岩芯样品所得的单烯烃类物质的离子峰的种类及其丰度列于表1。通过分析各峰位置及强度，借助有机物质标准质谱谱图，可快速确定该岩芯样品为含油矿石。
表1：检测岩芯样品所得的单烯烃类物质的离子峰的种类及其丰度
  m/z 99 m/z 113 m/z 127 m/z 141 m/z 155 m/z 169
有机成分 C7H14 C8H16 C9H18 C10H20 C11H22 C12H24
丰度/cps 9680 9600 21400 29700 33900 37800
  m/z 183 m/z 197 m/z 211 m/z 225 m/z 239 m/z 253
有机成分 C13H26 C14H28 C15H30 C16H32 C17H34 C18H36
丰度/cps 44800 60000 78200 72700 93000 102000
  m/z 267 m/z 281 m/z 295 m/z 309 m/z 323 m/z 337
有机成分 C19H38 C20H40 C21H42 C22H44 C23H46 C24H48
丰度/cps 123000 146000 179000 142000 142000 145000
  m/z 351 m/z 365 m/z 379 m/z 393 m/z 407 m/z 421
有机成分 C25H50 C26H52 C27H54 C28H56 C29H58 C30H60
丰度/cps 120000 97800 103000 84200 71300 69400
  m/z 435 m/z 449 m/z 463 m/z 477 m/z 491  
有机成分 C31H62 C32H64 C33H66 C34H68 C35H70  
丰度/cps 68800 54200 61900 48300 44300  
本实施例表明本发明微波等离子体炬外部烧蚀进样质谱分析结果准确，且等离子炬解吸电离过程仅需数秒，借助串联质谱数据，可在1分钟内给出质谱分析结果，可实现对矿石含有的有机成分的快速、准确分析，并进而能够判断其为何种可燃有机岩矿石，例如本例判断的为含油矿石。
实施例2：区分含油矿石和非含油矿石以及对可燃有机岩矿产的筛选
主成分分析(PCA)是一种化学计量学方法,它能够将复杂数据降维,从而起到排除噪音的效果,找到数据的最主要影响因素,目前该方法在复杂样品的分析检测中已得到广泛地应用。此处，利用实施例1的分析方法，对较多数量岩芯样品分别编号检测并收集一级质谱数据，由于含油矿石在其一级谱图含有许多质量相差14(CH2)的离子峰(如图2所示)，结合实施例1中鉴定出的有机物种类，可判断该类岩芯样品为含油矿石；而不含油的矿石中则没有这样的离子峰(如图3所示)，可判断该类岩芯样品为非含油矿石。将含油矿石的质谱分析数据作为第一组，将非含油矿石的质谱分析数据作为第二组，将两组数据导入MATLAB软件进行主成分分析，得到图4所示三维区分结果，在PCA三维得分图中，PC1，PC2，PC3分别为各个方向上对方差的贡献率，贡献率百分数数值越大，区分效果越明显，其中含油矿石(■表示的含油岩石)与非含油矿石(▲表示的非含油岩石)在图4中被明显区分。图4可作为含油矿石与不含油矿石的区分模型，表明采用微波等离子体炬质谱分析方法结合主成分分析可对含油矿石和不含油矿石样品进行快速区分。
图4的区分模型能应用在盲样中对含油矿石与非含油矿石进行区分：对大批量岩芯样品分别检测并收集各自质谱检测数据，将其标记为第三组“盲样”，结合第一组“含油矿石”的质谱分析数据、第二组“非含油矿石”的质谱分析数据，将三组数据导入MATLAB软件进行主成分分析，观察第三组盲样样品在PCA三维区分图(区分模型)中的落点，若某一盲样落点在含油矿石区域，则判定其为含油矿石；若落点在非含油矿石区域，则判定为非含油矿石。
利用该结果，一方面可以快速可靠地将含油矿石与非含油矿石进行区分，进而筛除不含油矿石，避免后续无谓而耗时的进一步分析；另一方面，结合各岩芯样品在地层中所处的位置，可以确定含油矿石在地层中的分布情况，帮助找油勘探。
显然，本实施例的岩芯样品还可以为煤、天然气等岩矿，在此不再赘述。可以理解的是，对于其它类型的可燃有机岩，“含油矿石”和“非含油矿石”仅作为区分的标记，“油”的概念应被理解为更宽泛的“有机物”。可见，本实施例的方法能应用于煤、石油、天然气等可燃有机岩矿产的普查与筛选，为能源勘探、开采和开发提供技术支持。
实施例3：对石油中有机物进行直接质谱分析
采用以上所述微波等离子体炬外部烧蚀进样对液体样品中有机物进行质谱分析。
样品：石油样本，液态。
分析包括以下步骤：
(1)将微波等离子体炬1与一质谱扫描仪的离子传输管进样口3置于同一竖向平面，且炬管头部开口端朝下与水面平成30°夹角(α)，微调微波等离子体1炬管的开口端与水平承载台上样品盘(表面皿)21之间的高度d1，以及与质谱仪进样口的距离d2；
(2)将载气11、辅助气12分别通入内管14和中管15，控制载气11的气体流速为800～1000mL/min，或至1200mL/min，控制辅助气12的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线17耦合至微波等离子体1炬管内，调整调谐活塞13以使在炬管的开口端可用金属丝引燃产生稳定的等离子体焰炬19；
(4)调整炬管1的位置，使产生的焰炬19尖端距表面皿21凹槽高d1约5mm，距质谱仪进样口d2约12mm；
(5)用移液枪将10μL的溶液样品滴入包裹有铝箔纸22的表面皿21的凹槽里；
(6)启动质谱扫描仪，保持焰炬19烧蚀约10s(利用微波等离子体炬的焰炬对其进行解吸和电离)，获取检测结果。
与实施例1类似，本实施例分析获得了该石油样品中的有机成分组成及其分布，可检测以及推测含油烷烃等有机成分，与该石油样品已知有机成分基本相同。
此外，采用以上所述微波等离子体炬外部烧蚀进样还可对液体样品对乙酰氨基酚滴剂中的有效成分进行直接质谱分析，操作过程类似，分析结果如图6所示。
本发明在该实施例中提出微波等离子体炬外部烧蚀进样针对液体样品进行质谱分析，结果准确，分析过程简单、快速。本实施例表明，本发明可实现对液体样品中有机物的快速、准确测定，可应用于石油、药品等的产品质控检测中。
气体样品的分析
对于气体样品，与对固体、液体样品的分析的不同之处在于进样方式不同。如图5所示，进样装置2为一输气管25，输气管25的入口连接待测气体样品，气 样出口26位于微波等离子体炬1焰炬19的下方d1位置且输气管25轴向与焰炬19轴向夹角β为60°-120°，利用微波等离子体炬1焰炬对输气管气样出口26的气体样品进行热解吸和电离，将气体样品中的有机物成分解吸出来并电离为各有机成分离子，并通过水平设置的质谱仪进样口3(与炬管轴向呈150°)进入质谱仪。
对气体样品分析的其它部分可以与前述完全相同，不再赘述。
以下结合具体实施例详细说明如何利用本发明对气体样品进行电离质谱分析。
实施例4：对天然气中有机成分进行直接质谱分析
采用以上所述微波等离子体炬质谱分析装置(采用图5所示进样装置)对气体样品中有机成分进行质谱分析。
样品：为天然气。
分析包括以下步骤：
(1)将微波等离子体炬1、输气管气样出口26与一质谱扫描仪的离子传输管进样口3置于同一竖向平面，输气管气样出口26朝上，炬管头部开口端朝下且与输气管气样出口26成60°夹角(β)，微调微波等离子体1炬管的开口端与输气管气样出口26之间的高度d1，以及与质谱仪进样口的距离d2；
(2)将载气11、辅助气12分别通入内管14和中管15，控制载气11的气体流速为800～1000mL/min，或至1200mL/min，控制辅助气12的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线17耦合至微波等离子体1炬管内，调整调谐活塞13以使在炬管的开口端可用金属丝引燃产生稳定的等离子体焰炬19；
(4)调整炬管1的位置，使产生的焰炬19尖端距输气管气样出口26的距离d1约3mm，距质谱仪进样口距离d2约10mm；
(5)向输气管25中通入安全用量的天然气；
(6)启动质谱扫描仪，保持焰炬19燃烧约10s(利用微波等离子体炬焰炬对样品进行解吸和电离)，获取检测结果。
分析获得了该天然气样品中的有机成分组成及其分布。本实施例表明，本发明可实现对气体样品中有机物的快速、准确测定，可应用于天然气等的产品质控检测中。
实施例5：对香烟烟雾中尼古丁进行直接质谱分析
采用以上所述微波等离子体炬质谱分析装置(采用图1所示进样装置)对香烟烟雾中尼古丁进行直接质谱分析。
样品：香烟烟雾，固体小颗粒与液体的混合物。
分析包括以下步骤：
(1)将微波等离子体炬1与一质谱扫描仪的离子传输管进样口3置于同一竖向平面，且炬管头部开口端朝下与水平面成30°夹角(β)，微调微波等离子体1炬管的开口端与水平承载台上样品盘21之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
(2)将载气11、辅助气12分别通入内管14和中管15，控制载气11的气体流速为800～1200mL/min，控制辅助气12的气体流速为200～400mL/min；
(3)打开一微波功率源，将微波通过耦合天线17耦合至微波等离子体1炬管内，调整调谐活塞13以使在炬管的开口端可用金属丝引燃产生稳定的等离子体焰炬19；
(4)调整炬管1的位置，使炬管产生的焰炬19尖端距样品盘21高d1约15mm，距质谱仪进样口d2约12mm；
(5)用镊子夹住香烟并置于样品盘21下方，移除样品盘21，此时香烟烟雾将自然向上漂浮至样品盘21所在位置并被MPT-MS分析检测；
(6)保持焰炬19烧蚀时间约10s(利用微波等离子体炬的焰炬对样品进行解吸和电离)，同时启动质谱扫描仪，获取检测结果。
香烟烟雾的质谱分析谱图如图7所示，可观察到离子m/z 163的强度最高，为111000cps。借助尼古丁标准质谱谱图，可确定该离子m/z 163为尼古丁的准分子离子峰。
本实施例表明本发明微波等离子体炬外部烧蚀进样质谱分析可对香烟烟雾中的尼古丁进行直接质谱分析，结果准确，且在一秒中内即可完成检测过程，可实现香烟烟雾中的尼古丁的快速、准确鉴定分析。
实施例6：对呼出气体中的酒精(乙醇)进行直接质谱分析
采用以上所述微波等离子体炬质谱分析装置(采用图5所示进样装置)对呼出气体中的酒精(乙醇)进行直接质谱分析。
样品：呼出气体。
分析包括以下步骤：
(1)将微波等离子体炬1、输气管气样出口26与一质谱扫描仪的离子传输管进样口3置于同一竖向平面，输气管气样出口26朝上，炬管头部开口端朝下且与输气管气样出口26成60°夹角(β)，微调微波等离子体1炬管的开口端与输气管气样出口26之间的高度d1，以及与质谱仪进样口的距离d2；
(2)将载气11、辅助气12分别通入内管14和中管15，控制载气11的气体流速为800～1200mL/min，控制辅助气12的气体流速为200～400mL/min；
(3)打开微波功率源，将微波通过耦合天线17耦合至微波等离子体1炬管内，调整调谐活塞13以使在炬管的开口端可用金属丝引燃产生稳定的等离子体焰炬19；
(4)调整炬管1的位置，使产生的焰炬19尖端距输气管气样出口26的距离d1约3mm，距质谱仪进样口距离d2约10mm；
(5)向输气管25中吹气；
(6)启动质谱扫描仪，保持焰炬19燃烧约10s(利用微波等离子体炬焰炬对样品进行解吸和电离)，获取检测结果。
本实施例表明本发明微波等离子体炬外部烧蚀进样质谱分析可对呼出气体中的酒精(乙醇)进行直接质谱分析，结果(如图8所示)准确，且在一秒中内即可完成检测过程，可实现呼出气体中的酒精(乙醇)的快速、准确鉴定分析。有望应用于判断司机是否酒后驾车的分析检测中。
此外，此方法还可用于检测呼出气体中的尼古丁、有机毒品等，应用于安全防护、缉毒侦查等特定需要的领域。
分析讨论
采用本发明方法，由微波等离子体炬1和质谱扫描仪3进行样品中有机物的质谱分析，无需对样品进行预处理，可直接对固体、液体和气体样品进行解吸、电离和质谱分析，分析速度快。
电离分析速度的快慢与微波等离子体炬中气体流速、微波源功率有关。载气、辅助气气体流速的大小影响焰炬的大小及其稳定性，通过调节载气输入和工作气输入流量的大小来得到稳定的焰炬。其中，载气流量对信号强度有较大的影响。当载气流量过小时，形成的等离子体将样品解吸电离后进入质谱的速度也会相应变慢。当载气流量过大时，形成的等离子体与样品作用后容易被气流吹散迸溅，检测结果不佳，本发明选择载气流速为800～1200mL/min。同样，工作气(辅助 气体)流量也对检测结果有影响，工作气体流量小时等离子体的体积小，样品与等离子体作用不充分，信号强度小；工作气体流量过大时，一方面对等离子体有冷却作用使其温度降低不利于样品激发，另一方面等离子体的一部分能量将会消耗在激发氩原子上从而使信号强度变小。本发明选择工作气流速为200～400mL/min。
微波源功率在0～200W内可调，在高微波源功率条件下，产生的焰炬因温度过高，使大部分样品被烧蚀分解，解吸和电离得到待测成分的离子峰相对丰度较低，强度较弱。本发明确定的功率为30～50W，此时，微波等离子体炬管的开口端用金属丝引燃出口的中性气体产生焰炬。焰炬为等离子体流，其与样品作用能将样品中有机物解吸和电离成为带电粒子流，并引入质谱扫描仪中开始记录数据，整个分析过程需要的时间为10s左右。
另外，采用本发明的等离子体炬电离质谱分析，电离效率高，电离分析时样品消耗量少、分析速度快，对于高成本或稀有样品来说，分析成本显著降低。
工业应用性
本发明微波等离子体炬质谱分析装置结合了微波等离子体炬和质谱扫描仪，能够制造和使用，微波等离子体炬质谱分析方法能对固体、液体、气体不同样态的样品进行快速、准确分析，可用于煤、石油、天然气等矿产中有机成分的检测以实现对可燃有机岩矿产的普查与筛选，能在工业中进行应用。

Claims (17)

  1. 微波等离子体炬质谱分析装置，包括大气压环境下工作的进样装置、微波等离子体炬、微波源和质谱仪，所述微波等离子体炬既为电离源也为解吸装置，进样装置的样品端、微波等离子体炬炬焰和质谱仪进样口在同一垂直平面分布，微波等离子体炬炬管头部开口端朝下以一夹角指向样品端，炬焰尾部与样品端高度为d1，与质谱仪进样口的水平距离为d2。
  2. 根据权利要求1所述微波等离子体炬质谱分析装置，所述样品为固体或液体，所述进样装置包括水平放置的样品盘和包覆该样品盘的铝箔纸，样品置于铝箔纸上；质谱仪进样口与样品盘在同一水平面上，微波等离子体炬炬管轴向与水平放置的样品盘夹角α为30°-60°，d1≤5mm，d2约为8-12mm。
  3. 根据权利要求2所述微波等离子体炬质谱分析装置，所述样品为固体，所述样品盘为平盘或表面皿。
  4. 根据权利要求2所述微波等离子体炬质谱分析装置，所述样品为液体，所述样品盘为表面皿。
  5. 根据权利要求1所述微波等离子体炬质谱分析装置，所述样品为气态，所述进样装置为一输气管，输气管的入口连接待测气体样品，气样出口位于微波等离子体炬焰炬的下方d1位置，d1≤5mm，且气样出口轴向与微波等离子体炬炬管轴向夹角β为45°-120°，d2约为5-10mm。
  6. 根据权利要求1至5任一所述微波等离子体炬质谱分析装置，所述微波等离子体炬管由同轴装配的内管、中管和外管构成腔体部分，腔体部分开口端产生焰炬，尾部设置有调谐活塞。
  7. 根据权利要求6所述微波等离子体炬质谱分析装置，内管中通入载体，中管中通入辅助气体，载气和辅助气体均为中性气体，包括氩气、氦气等惰性气体或氮气，中性气体在腔体部分的开口端被激发形成等离子体。
  8. 根据权利要求6或7所述微波等离子体炬质谱分析装置，外管壁上开设有一微波耦合开口，耦合环固定在该微波耦合开口处的中管外壁上，耦合天线穿过该微波耦合开口与耦合环连接，耦合天线与装置外的微波传输线连接，将微波耦合传输至外管和中管之间从而在外管和中管间形成微波谐振腔。
  9. 根据权利要求6或7或8所述微波等离子体炬质谱分析装置，所述调谐活塞为一“工”字型中空的套件，其中空段套于炬管尾部的中管外壁，工字底部为内端面作为微波反射面，位于炬管外管内侧尾部，工字上部为外端面作为操作面， 位于炬管外管尾部外侧；借助推动外端面使调谐活塞整体能沿中管轴向滑动，并由外管尾端外壁对滑动距离限位。
  10. 一种微波等离子体炬质谱分析方法，大气压环境下安装权利要求1至9任一项所述的微波等离子体炬质谱分析装置，向微波等离子体的内管和中管中通入中性气体，利用耦合天线将微波耦合至微波等离子体炬管内，并在炬管的开口端用金属丝引燃产生焰炬；调整微波等离子体炬炬管与样品端的夹角α以及d1和d2大小，引入待测样品，保持焰炬烧蚀时间将样品中待测有机成分解吸并电离，同时启动质谱扫描仪，获取有机成分质谱检测数据并完成样品质谱分析。
  11. 根据权利要求10所述微波等离子体炬质谱分析方法，针对固体样品检测包括以下过程：
    (1)将微波等离子体炬与质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水面平成30°～60°夹角(α，较好为30°～45°)，微调微波等离子体炬管的开口端与水平承载台上样品盘之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
    (2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min，控制辅助气的气体流速为200～400mL/min；
    (3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
    (4)调整炬管的位置，使炬管产生的焰炬尖端距样品盘高d1≤5mm(较好约1～3mm)，距质谱仪进样口d2约8～12mm(较好为10mm)；
    (5)将固体样品置于包裹有铝箔纸的样品盘上；
    (6)启动质谱扫描仪，保持焰炬烧蚀时间约10s，获取检测结果。
  12. 根据权利要求10所述微波等离子体炬质谱分析方法，针对液体样品检测包括以下过程：
    (1)将微波等离子体炬与一质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水面平成30°～60°夹角(α，较好为30°)，微调微波等离子体炬管的开口端与表面皿之间的高度d1，以及与质谱仪进样口的距离d2；
    (2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min，控制辅助气的气体流速为200～400mL/min；
    (3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
    (4)调整炬管的位置，使产生的焰炬尖端距表面皿凹槽高d1≤5mm(较好约 3～5mm)，距质谱仪进样口d2约8～12mm(较好为12mm)；
    (5)用移液枪将10μL的溶液样品滴入包裹有铝箔纸的表面皿的凹槽里；
    (6)启动质谱扫描仪，保持焰炬烧蚀约10s，获取检测结果。
  13. 根据权利要求10所述微波等离子体炬质谱分析方法，针对烟雾检测包括以下过程：
    (1)将微波等离子体炬与质谱扫描仪的离子传输管进样口置于同一竖向平面，且炬管头部开口端朝下与水平面成30°夹角(α)，微调微波等离子体炬管的开口端与样品盘之间的高度(d1)，以及与质谱仪进样口的距离(d2)；
    (2)将载气、辅助气分别通入内管和中管，控制载气的气体流速为800～1200mL/min，控制辅助气的气体流速为200～400mL/min；
    (3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
    (4)调整炬管的位置，使炬管产生的焰炬尖端距样品盘高d1约15mm，距质谱仪进样口d2约12mm；
    (5)将香烟正在燃烧的头部置于包裹有铝箔纸的样品盘上，或直接将香烟正在燃烧的头部置于样品盘所在的位置处代替样品盘，使香烟烟雾自然向上漂浮；
    (6)启动质谱扫描仪，保持焰炬烧蚀约10s，获取检测结果。
  14. 根据权利要求10所述微波等离子体炬质谱分析方法，针对气态样品检测包括以下过程：
    (1)将微波等离子体炬、输气管气样出口与质谱扫描仪的离子传输管进样口置于同一竖向平面，输气管气样出口朝上，炬管头部开口端朝下且与输气管气样出口夹角β为45°-120°(优选60°)，微调微波等离子体炬管的开口端与输气管气样出口之间的高度d1，以及与质谱仪进样口的距离d2；
    (2)将载气、辅助气分别通入内管和中管，控制载气11的气体流速为800～1200mL/min，控制辅助气12的气体流速为200～400mL/min；
    (3)打开微波功率源，将微波通过耦合天线耦合至微波等离子体炬管内，调整调谐活塞，在炬管的开口端用金属丝引燃产生稳定的等离子体焰炬；
    (4)调整炬管的位置，使产生的焰炬尖端距输气管气样出口26的距离d1≤5mm(优选约3mm)，距质谱仪进样口距离d2约为5～10mm(优选8～10mm)；
    (5)向输气管中通入气态样品或向输气管中呼气；
    (6)启动质谱扫描仪，保持焰炬燃烧约10s，获取检测结果。
  15. 根据权利要求10至14任一所述的微波等离子体炬质谱分析方法，所述载气和辅助气均为中性气体，中性气体为惰性气体或氮气。
  16. 区分含油矿石和非含油矿石的方法，包括以下步骤：
    1)利用权利要求10或11所述微波等离子体炬质谱分析方法对批量岩芯样品分别检测并收集各自质谱检测数据，将一级谱图含有质量相差14(CH2)的离子峰的样品标记为“含油矿石”，将没有这样的离子峰的样品标记为“非含油矿石”；
    2)对待检测的大批量岩芯样品分别检测并收集各自质谱检测数据，将其标记为“盲样”，将含油矿石的质谱检测数据、非含油矿石的质谱检测数据、盲样的质谱检测数据共三组数据采用主成分分析法进行分析，得到能区分含油矿石区域和非含油矿石区域的PCA三维得分图；
    3)将在PCA三维得分图中落点位于含油矿石区域的盲样判定为含油矿石，将落点位于非含油矿石区域的盲样判定为非含油矿石。
  17. 对可燃有机岩矿产的快速普查与筛选方法，所述岩芯样品为可燃有机岩，包括煤、石油、天然气等岩石或矿石，该筛选方法首先利用权利要求16所述方法区分含油矿石和非含油矿石，然后将判定为“非含油矿石”的样品筛除。
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