(19)
(11)EP 2 889 615 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.07.2020 Bulletin 2020/31

(21)Application number: 14199450.9

(22)Date of filing:  19.12.2014
(51)International Patent Classification (IPC): 
G01N 30/12(2006.01)
G01N 30/30(2006.01)
G01N 30/20(2006.01)
G01N 30/18(2006.01)
G01N 30/72(2006.01)

(54)

Vaporizing injector, gas chromatograph and combined spectrometer

Verdampfungsinjektor, Gaschromatograf und kombiniertes Spektrometer

Injecteur avec vaporisation d'échantillon, chromatographe en phase gazeuse et spectromètre combiné


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 30.12.2013 CN 201310746569

(43)Date of publication of application:
01.07.2015 Bulletin 2015/27

(73)Proprietor: Nuctech Company Limited
TongFang Building, Shuangqinglu, Haidian District Beijing 100084 (CN)

(72)Inventors:
  • Zhang, Qingjun
    100084 Bejing (CN)
  • Li, Yuanjing
    100084 Bejing (CN)
  • Chen, Zhiqiang
    100084 Bejing (CN)
  • Ma, Qiufeng
    100084 Bejing (CN)
  • Zhao, Ziran
    100084 Bejing (CN)
  • Liu, Yinong
    100084 Bejing (CN)
  • Wang, Junxiao
    100084 Bejing (CN)
  • Zou, Xiang
    100084 Bejing (CN)
  • Wang, Yanchun
    100084 Bejing (CN)
  • Chang, Jianping
    100084 Bejing (CN)
  • Tan, Linxia
    100084 Bejing (CN)
  • Liu, Yaohong
    100084 Bejing (CN)

(74)Representative: Dilg, Haeusler, Schindelmann Patentanwaltsgesellschaft mbH et al
Leonrodstraße 58
80636 München
80636 München (DE)


(56)References cited: : 
CN-A- 1 352 390
US-A- 5 954 862
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention belongs to the field of analysis and detection, and relates to a sample injector for a gas chromatography or a gas chromatography- ion mobility spectrometer and particularly to a split/splitless programmed temperature sample injector for capillary columns.

    Background



    [0002] During the analysis process of a sample by using Gas Chromatography (GC) or a GC combined to ion mobility spectrometer (IMS)/Mass Spectrometer (MS), the sample passes through a sample injector first. The sample injector is used for rapid vaporizing the liquid or solid sample of interest at a first place and then feeding the sample vapor to a GC column head quickly, accurately and quantitatively after mixing and diluting with the carrier gas. Since the first capillary column has been produced by Perkin Elmer, due to its advantages of high column efficiency and good separation performance, there has been already more than 90% of GC analysis realized by capillary columns nowadays ("Basic Gas Chromatography", Second Edition, by Harold M. McNair and James M. Miller. Copyright © 2009 John Wiley & Sons, Inc.). Due to the characteristic of small capacity of a capillary column itself, split/splitless sample injectors have become the most common sample injectors for GC, GC-IMS or GC-MS.

    [0003] There have been mature split/splitless sample injectors at present. However, as different sample components have different actual split ratios, under a certain set separation ratio, the component entering a chromatographic column (capillary column) will be different from the original sample component so as to result in split discrimination (especially for samples having a wide boiling range), so that the accuracy of analysis is influenced to result in poor quantification and complexity.

    [0004] There are mainly three aspects for the cause of the split discrimination:

    First, non-uniform heating temperature distribution of a vaporizingchamber: in some cases, a difference between the temperature at the center of the vaporizing chamber and the temperature at two ends thereof is very large, so the sample is not vaporized uniformly or components having different boiling points are coagulated at positions below the point of vaporization point after being vaporized.

    Second, the carrier gas is not preheated: the carrier gas will have a change in temperature gradient after entering the vaporizing chamber, so the vaporization rates of different components of the sample will be different; as the time the sample enters the chromatographic column from vaporizing in the vaporizing chamber is very short (in seconds), so that the split flow is far larger than the flow in the column, and thus the components not fully vaporized may split more samples than the components fully vaporized.

    Third, different sample components have different diffusion rates in the carrier gas; however, the diffusion rate is in direct proportion to the temperature, so vaporizing the sample as quick as possible is an important measure for reducing split discrimination. Therefore, the temperature of the sample injector must be strictly controlled and is slightly higher than the temperature of the column oven; thus, the manufacturing cost of the sample injector is improved, and it is disadvantageous for the analysis of thermally instable substances.



    [0005] Patent No. CN1352390A has disclosed a sample injector for solving the preheating problem of carrier gas. In the sample injector, a carrier gas preheating chamber is provided between a split flow exporting channel and a vaporizing chamber, a carrier gas inlet is communicated with the lower portion of the carrier gas preheating chamber, and the upper portion of the carrier gas preheating chamber is communicated with the vaporizing chamber. The carrier gas enters the carrier gas preheating chamber from the inlet and then moves upward after preheated, and then enters the vaporizing chamber from the top to contact a sample and vaporize the sample instantly. Although such a sample injector port solves the preheating problem of carrier gas and the problem of split discrimination, the volume of the vaporizing chamber is increased equivalently as the preheating chamber is communicated with the vaporizing chamber, that is, the pre-column dead volume is increased. Thus, the vaporized sample mixture gas will be diffused back to the preheating chamber, thereby increasing retention time (RT) and broadening peak.

    [0006] To overcome the problems in the patent CN1352390A, Patent No. CN203216933U has disclosed a sample injector for non-volatile substances, including a shell and a diffusion tube disposed inside the shell. A carrier gas channel communicated with the diffusion tube is provided on an end cover of the shell. The carrier gas channel extends to the inside of the diffusion tube and has a certain distance away from the bottom of the diffusion tube. The advantage of this design is that, as the sample is placed on the bottom of the diffusion tube, the volatilization concentration on the surface is the highest during the volatilization of the sample; and the carrier gas channel extends above the surface of the sample, so the carrier gas may take away all the volatilized gas on the surface of the sample. In order to uniformly heat the upper and lower portions of the sample injector, electric bars extending from the bottom of the shell to the end cover are uniformly arranged around the shell of the sample injector, so that uniform heating of the upper and lower portions of the sample injector is realized. In the parent, the problem of non-uniform vaporizing of the sample is solved, but the sample injector has a splitless mode only. As the splitless sample injection mode has complicated operating conditions and high requirements for operation techniques, the splitless sample injection is far less common than the split sample injection in practice. Therefore, the splitless sample injection is taken into consideration only when the split sample injection cannot meet the analysis requirements (mainly requirements for sensitivity).

    [0007] US5954862 discloses a Programmed Temperature Vaporizing (PTV) injector suitable for split/ splitless injection, and provided with a carrier gas channel, a purge channel and heating means.

    [0008] In addition, it is required to perform continuous sample injection when a detection task is heavy, and it is required to reset temperature of a sample injector in the case of an obvious difference between boiling ranges of samples at two adjacent times. Although there are various split/splitless sample injectors of different types, yet there are few general sample injectors capable of cooling fast. Therefore, in order to realize fast testing, it is necessary to add a fast cooling design and a temperature control design to a general sample injector.

    Summary



    [0009] To solve the problems in the prior art, an objective of the present invention is to provide a general sample injector having simple structure, fast continuous sample injection and good detection effect on samples with a wide boiling range. The inventor recognized that the uniform temperature of a vaporizing chamber, the preheating of carrier gas and the full mixture of samples may eliminate split discrimination.

    [0010] To achieve the above objective, according to one aspect of the present invention, a sample injector according to claim 1 is provided. The sample injector includes a sample injector shell and a vaporizing chamber located in the sample injector shell;
    a sample injector shell opening and a detachable end cover are arranged at the top of the sample injector shell, and the end cover seals the sample injector shell opening;
    a vaporizing chamber opening is arranged at the top of the vaporizing chamber, and a channel for enabling a gas to pass is reserved between the vaporizing chamber opening and the end cover;
    a carrier gas channel, a septum purge channel and a coolant channel are further arranged in the sample injector shell along the outer circumference of the vaporizing chamber, a carrier gas channel opening portion and a septum purge channel opening portion are respectively arranged at the tops of the carrier gas channel, the coolant channel and the septum purge channel, and both of the carrier gas channel opening portion and the septum purge channel opening portion are communicated with the opening at the top of the vaporizing chamber; the carrier gas channel is provided with a carrier gas inlet, the septum purge channel is provided with a septum purge channel outlet, and the coolant channel is provided with a coolant inlet and a coolant outlet;
    a capillary column is arranged at the bottom of the vaporizing chamber, one end of the capillary column projects into the vaporizing chamber, and the other end of the capillary column projects out of the sample injector;
    a heater is further arranged in the sample injector shell.

    [0011] Preferably, a inlet liner is fixed in the vaporizing chamber, the two ends of the inlet liner are open, the opening at the top of the inlet liner is communicated with the opening at the top of the vaporizing chamber, and the opening at the bottom of the inlet liner is not in contact with the bottom of the vaporizing chamber;
    a gap for enabling the gap to pass is reserved between the outer surface of the inlet liner and the inner surface of the vaporizing chamber;
    a ring-shaped sealing and fixing device is arranged at the outer edge of the opening at the top of the inlet liner and at the inner edge of the opening of the vaporizing chamber; the inlet liner penetrates through the ring-shaped sealing device to fix the outer edge of the opening at the top of the inlet liner in the vaporizing chamber.

    [0012] Preferably, the sealing ring is made from a high temperature resistant rubber material or a graphite material.

    [0013] Preferably, the sample injector further includes a flow splitting channel, the flow splitting channel is provided with a flow splitting channel opening and a flow splitting channel outlet, and the flow splitting channel opening is arranged on the side wall of the vaporizing chamber and is communicated with the vaporizing chamber. Preferably, the coolant channel is further communicated with the vaporizing chamber. Preferably, a sealing septum is further arranged between the sample injector shell opening and the detachable end cover, and a channel for enabling the gas to pass is reserved between the sealing septum and the vaporizing chamber opening.

    [0014] Preferably, the carrier gas inlet, the septum purge channel outlet, the coolant inlet and the coolant outlet are all arranged at the bottom of the sample injector shell.

    [0015] According to the present invention, the inlet of the carrier gas channel, the outlet of the septum purge channel and the inlet and the outlet of the coolant channel are all connected with a gas flow control valve.

    [0016] According to the present invention, the heaters are uniformly distributed on the outer wall of the sample injector shell, a temperature control unit is further included, and the heaters are controlled by the temperature control unit to achieve single-point heating or programmed temperature heating.

    [0017] According to the present invention, the inlet of the carrier gas channel, the outlet of the septum purge channel and the inlet and the outlet of the coolant channel are all connected with the gas flow control valve, and the temperature control unit is further connected with the gas flow control valve; the temperature control unit and the gas flow control valve cooperate to cool the sample injector.

    [0018] Preferably, the sample injector shell is made from a metallic material, and the center of the end cover and the center of the vaporizing chamber are coaxial.

    [0019] Preferably, the capillary column is arranged just at the central position of the bottom of the vaporizing chamber.

    [0020] The coolant channel functions as refrigerating and cooling the vaporizing chamber. During cooling, the coolant having large thermal capacity, including liquid nitrogen, liquid CO2 or water, may be employed, or heat dissipation may be realized directly by nitrogen in atmosphere or air. When the liquid nitrogen or nitrogen is used for cooling, the coolant channel is communicated with the vaporizing chamber, and the coolant enters the vaporizing chamber from the coolant channel and flows along the flow splitting channel, the septum purge channel and a coolant outlet channel, so that the coolant plays a role of cooling and also purging the vaporizing chamber. When the non-inert coolant is used for cooling, the coolant channel undergoes reflux on the sample injector shell and is not communicated with the vaporizing chamber. The heater is uniformly distributed on the outer wall of the sample injector shell, so that the uniform heating of the upper and lower portions of the sample injector is ensured.

    [0021] The sample injector, equivalent to a programmed temperature injector combining splitting/no splitting with cold column head sample injection, gives full play to the advantages of various sample injection modes, overcomes a plurality of disadvantages, and has higher practicability and better flexibility.

    [0022] According to another aspect of the present invention, a gas chromatograph is further disclosed. The gas chromatograph includes the sample injector according to any one of the above embodiments

    [0023] According to still another aspect of the present invention, a gas chromatography- ion mobility spectrometer is further disclosed. The gas chromatography- ion mobility spectrometer includes the sample injector according to any one of the above embodiments.

    [0024] According to a further aspect of the present invention, a gas chromatography-mass spectrum combined spectrometer is further disclosed. The combined spectrometer includes the sample injector according to any one of the above embodiments.

    [0025] The sample injector, the gas chromatography and the combined spectrometer provided by the present invention have the following significant technical effects:
    1. 1. A plurality of channels are provided in the length direction of the vaporizing chamber, and one of the channels is used as a carrier gas channel, so the carrier gas may be preheated to have enough thermal capacity before entering the vaporizing chamber, so that it is ensured that the sample is quickly and uniformly vaporized after entering the vaporizing chamber and then enters a capillary column, thereby reducing split discrimination and obtaining better results of detection.
    2. 2. Other channels used as a coolant channel, a septum purge channel and a flow splitting channel respectively are also disposed on the sample injector shell. The advantage of this design is that the thermal capacity of the metal shell is reduced by the plurality of channels, and the coolant and flowing on the sample injector shell carrier gas may take away the heat of the vaporizing chamber and thus cool the vaporizing chamber. By this design, both quick heating and quick cooling may be realized, and it is advantageous for quick continuous sample injection during processing a large number of detection tasks.
    3. 3. The heater of the sample injector provided by the present invention is uniformly distributed on the sample injector shell. The advantage of such a design is that the sample injector shell may be uniformly heated, quick heating may be realized, the uniform vaporizing of the sample may be ensured, and the split discrimination is reduced.
    4. 4. The coordinative control of the coolant channel, the multichannel airflow control valve and the temperature controller allows the sample injector to have a programmed temperature function. As different samples are different in volatility, a low temperature needs to be set to first volatilize some volatile substances or substances easy to crack at a high temperature, while non-volatile samples are heated to a high temperature for volatilization, so as to make each sample component reach the optimal volatilization. The detection of a sample having a wide boiling range may employ programmed temperature vaporizer injection, so the substances easy to thermally crack or coke may be effectively protected. The advantage of this design is that the sample injection, as a general sample injector for use, may effectively realize the analysis of a sample having a wide boiling range and eliminates split discrimination.

    Brief Description of the Drawings



    [0026] Fig. 1 is a structure diagram of a sample injector according to an embodiment of the present invention.

    [0027] Reference numerals in Fig. 1: 1-End cover; 2- sealing septum; 3-Sample injector shell; 4-Seal ring; 5-Vaporizing chamber; 6-Inlet liner; 7-Carrier gas channel; 8-Septum purge channel; 9-Flow splitting channel; 10-Coolant channel; 11-Coolant inlet; 12-Gas source inlet; 13-Mutichannel flow control valve; 14-Carrier gas inlet; 15-Split flow outlet; 16-Septum purge gas outlet; 17-Coolant outlet; 18-Main gas outlet; 19-Capillary column; 20-Heater; 21-Temperature controller; 22-Cross section of sample injector shell.

    Detailed Description of the Preferred Embodiments



    [0028] The specific embodiments of the present invention are further described below in detail in conjunction with the accompanying drawings and the embodiments. The embodiments below are only used for illustrating the present invention, rather than limiting the scope of the present invention.

    [0029] As shown in Fig.1, the present invention provides a sample injector, including: a sample injector shell and a vaporizing chamber located in the sample injector shell; a sample injector shell opening and a detachable end cover are arranged at the top of the sample injector shell, and the end cover seals the sample injector shell opening; a vaporizing chamber opening is arranged at the top of the vaporizing chamber, and a channel for enabling a gas to pass is reserved between the vaporizing chamber opening and the end cover; a carrier gas channel, a septum purge channel and a coolant channel are further arranged in the sample injector shell along the outer circumference of the vaporizing chamber, a carrier gas channel opening portion and a septum purge channel opening portion are respectively arranged at the tops of the carrier gas channel, the coolant channel and the septum purge channel, and both of the carrier gas channel opening portion and the septum purge channel opening portion are communicated with the opening at the top of the vaporizing chamber; the carrier gas channel is provided with a carrier gas inlet, the septum purge channel is provided with a septum purge channel outlet, and the coolant channel is provided with a coolant inlet and a coolant outlet; a capillary column is arranged at the bottom of the vaporizing chamber, one end of the capillary column projects into the vaporizing chamber, and the other end of the capillary column projects out of the sample injector; a heater is further arranged in the sample injector shell. A detailed description of the sample injector provided by the present invention will be given below.

    [0030] Referring to Fig. 1, according to an embodiment of the present invention, a sample injection port mechanism of a sample injector is located on the top of the sample injector and consists of an end cover 1 and a sealing septum 2. The end cover 1 is sheathed on a sample injector shell 3 through threads, so it is convenient for disassembling and convenient to place a disposable sample tube during sample injection of solid. A channel for enabling the gas to pass is reserved between the sealing septum and the vaporizing chamber opening.

    [0031] The vaporizing chamber 5 is located inside the sample injector shell, a sealing septum 2 for sealing the vaporizing chamber and the sample injection port is provided between the vaporizing chamber 5 and the end cover 1, and the center of the end cover is coaxial with the center of the vaporizing chamber. When a gas or liquid sample is injected, a quartz or glass inlet liner may be placed inside the vaporizing chamber. When a solid sample is injected, a disposable sample tube with solid component absorbed thereon may be placed inside the vaporizing chamber. The two ends of the inlet liner are open, the opening at the top of the inlet liner is communicated with the opening at the top of the vaporizing chamber, and the opening at the bottom of the inlet liner is not in contact with the bottom of the vaporizing chamber; a gap for enabling the gap to pass is reserved between the outer surface of the inlet liner and the inner surface of the vaporizing chamber; a ring-shaped sealing and fixing device is arranged at the outer edge of the opening at the top of the inlet liner and at the inner edge of the opening of the vaporizing chamber; the inlet liner penetrates through the ring-shaped sealing device to fix the outer edge of the opening at the top of the inlet liner in the vaporizing chamber. Specifically:
    The inlet liner or disposable sample tube 6 is tightly sealed and supported by an O-shaped seal ring 4 and placed at the middle of the vaporizing chamber 5.

    [0032] A capillary column 19 is provided at the right center of the bottom of the vaporizing chamber 5. The capillary column 19 is fixed on the bottom of the vaporizing chamber via a seal gasket and a nut convenient to be disassembled.

    [0033] A plurality of channels is uniformly provided inside the sample injector shell 3 along the outer circumference of the vaporizing chamber. The positions of the channels may be observed with reference to the cross section 22 of the sample injector shell. The outlets and inlets of all the channels are formed on the bottom of the sample injector shell and extend to the upper end of the sample injector along the length direction of the vaporizing chamber. The plurality of channels may be functionally divided into a carrier gas channel 7, a septum purge channel 8, a flow splitting channel 9 and a coolant channel 10, wherein a carrier gas inlet 14 is connected to a gas source inlet 12 via a valve, the carrier gas flows upward from the carrier gas inlet 14 on the bottom of the sample injector shell along the carrier gas channel, and then enters the vaporizing chamber from the inlet of the vaporizing chamber 5 after preheated; the septum purge channel 8 is communicated with the opening at the top of the vaporizing chamber and leads out from a septum purge outlet 16 on the bottom of the sample injector shell in the length direction of the sample injector shell; the flow splitting channel 9 enters the top of the vaporizing chamber through a clearance between the vaporizing chamber 5 and the inlet liner 6 from the bottom of the inlet liner, extends out from the vaporizing chamber 5 from the underneath of the seal ring 4 and leads out from the bottom split flow outlet 15 along the flow splitting channel on the sample injector shell. The coolant channel 10 is uniformly distributed around the vaporizing chamber 5. To achieve the purpose of quick cooling, the coolant channel is communicated with the vaporizing chamber. The coolant may enter the coolant channel 10 from a coolant inlet 11. When liquid nitrogen, nitrogen or other inert substances are used for cooling, the coolant channel 10 may be communicated with the vaporizing chamber, the coolant and the carrier gas simultaneously enter the vaporizing chamber for cooling the vaporizing chamber, and the coolant may flow out from a coolant outlet 17 along the septum purge channel 8, the flow splitting channel 9 and the coolant channel 10, so that the coolant plays roles of cooling the vaporizing chamber and also purging the vaporizing chamber. When other non-inert cooling substances are employed, the coolant channel 10 is an independent reflux channel, is not communicated with the vaporizing chamber 5, and plays a role of cooling only. The working states and working time sequences of the channels are realized by a multichannel airflow control valve 13. A main gas outlet 18 used for discharging gas is connected to the outlets of the plurality channels via the multichannel airflow control valve 13.

    [0034] The heater 20 is uniformly distributed on the outer wall of the sample injector shell, so that uniform heating of the upper and lower portions of the sample injector is ensured. The heater 20 is controlled by the temperature control unit 21 to realize single-point heating or programmed temperature heating. The coordinative effect of the temperature control unit 21 and the multichannel airflow control valve 13 realizes the cooling of the sample injector. During detection of a sample having a wide boiling range, the programmed temperature function may be activated for sample injection, so that the cracking or coking of low boiling point positions may be effectively avoided, split discrimination may also be overcome, and the accuracy of the results of detection is ensured.

    [0035] Preferably, the seal ring is made from high temperature resistant rubber material or graphite material, and the heater is a resistance wire or a mica sheet.

    [0036] According to another aspect of the present invention, a gas chromatograph is further disclosed. The gas chromatograph includes the sample injector according to any one of the above embodiments

    [0037] According to another aspect of the present invention, a gas chromatography- ion mobility spectrometer is further disclosed, which includes the sample injector according to any one of the above embodiments.

    [0038] According to another aspect of the present invention, a gas chromatography-mass spectrum combined spectrometer is further disclosed. The gas chromatography-mass spectrum combined spectrometer includes the sample injector according to any one of the above embodiments.

    [0039] The foregoing specific embodiments are merely used for explaining the technical solutions of the present invention, but the present invention is not limited thereto. All improvements and substitutions of the above principle and based on the present invention shall fall into the protection scope of the present invention.

    [0040] To sum up, the sample injector, the gas chromatography and the combined spectrometer provided by the present invention have the following significant technical effects: 1. A plurality of channels are provided in the length direction of the vaporizing chamber, and one of the channels is used as a carrier gas channel, so the carrier gas may be preheated to have enough thermal capacity before entering the vaporizing chamber, to ensure that the sample is quickly and uniformly vaporized after entering the vaporizing chamber and then enters a capillary column, thereby reducing split discrimination and obtaining better results of detection. 2. Other plurality of channels used as a coolant channel, a septum purge channel and a flow splitting channel respectively are also disposed on the sample injector shell. The advantage of this design lies in that on the one hand, the thermal capacity of the metal shell is reduced by the plurality of channels, and on the other hand, the coolant and flowing on the sample injector shell and the carrier gas can take away the heat of the vaporizing chamber and thus cool the vaporizing chamber. By this design, both quick heating and quick cooling can be achieved, and it is advantageous for quick continuous sample injection during processing a large number of detection tasks. 3. The heater of the sample injector provided by the present invention is uniformly distributed on the sample injector shell. The advantage of such a design is that the sample injector shell may be uniformly heated, quick heating may be realized, the uniform vaporizing of the sample may be ensured, and the split discrimination is reduced. 4. The coordinative control of the coolant channel, the multichannel airflow control valve and the temperature controller allows the sample injector to have a programmed temperature function. As different samples are different in volatility, a low temperature needs to be set to first volatilize some volatile substances or substances easy to crack at a high temperature, while non-volatile samples are heated to a high temperature for volatilization, so as to make each sample component reach the optimal volatilization. The detection of a sample having a wide boiling range may employ programmed temperature vaporizer injection, such that the substances easy to thermally crack or coke may be effectively protected. The advantage of this design is that the sample injection, as a sample injector for use, may effectively realize the analysis of a sample having a wide boiling range and eliminates split discrimination.

    Industrial Applicability



    [0041] To sum up, the sample injector, the gas chromatography and the combined spectrometer provided by the present invention have the following willful technical effects: 1. A plurality of channels are provided in the length direction of the vaporizing chamber, and one of the channels is used as a carrier gas channel, so the carrier gas may be preheated to have enough thermal capacity before entering the vaporizing chamber, so as to ensure that the sample is quickly and uniformly vaporized after entering the vaporizing chamber and then enters a capillary column, thereby reducing split discrimination and obtaining better results of detection. 2. Other plurality of channels used as a coolant channel, a septum purge channel and a flow splitting channel respectively are also disposed on the sample injector shell. The advantage of this design lies in that one the one hand, the thermal capacity of the metal shell is reduced by the plurality of channels, and on the other hand, the coolant and flowing on the sample injector shell and the carrier gas can take away the heat of the vaporizing chamber and thus cool the vaporizing chamber. By this design, both quick heating and quick cooling can be achieved, and it is advantageous for quick continuous sample injection during processing a large number of detection tasks. 3. The heater of the sample injector provided by the present invention is uniformly distributed on the sample injector shell. The advantage of such a design is that the sample injector shell may be uniformly heated, quick heating may be realized, the uniform vaporizing of the sample may be ensured, and the split discrimination is reduced. 4. The coordinative control of the coolant channel, the multichannel airflow control valve and the temperature controller allows the sample injector to have a programmed temperature function. As different samples are different in volatility, a low temperature needs to be set to first volatilize some volatile substances or substances easy to crack at a high temperature, while non-volatile samples are heated to a high temperature for volatilization, so as to make each sample component reach the optimal volatilization. The detection of a sample having a wide boiling range may employ programmed temperature vaporizer injection, so the substances easy to thermally crack or coke may be effectively protected. The advantage of this design is that the sample injection, as a general sample injector for use, may effectively realize the analysis of a sample having a wide boiling range and eliminates split discrimination.


    Claims

    1. A sample injector, comprising a sample injector shell (3) and a vaporizing chamber (5) located in the sample injector shell (3), wherein:

    a sample injector shell opening and a detachable end cover (1) are arranged at the top of the sample injector shell (3), and the end cover (1) seals the sample injector shell opening;

    a vaporizing chamber opening is arranged at the top of the vaporizing chamber (5), and a channel for enabling a gas to pass is reserved between the vaporizing chamber opening and the end cover (1);

    a carrier gas channel (7), a septum purge channel (8) and a coolant channel (10) are further arranged in the sample injector shell (3) along the outer circumference of the vaporizing chamber (5), a carrier gas channel opening portion and a septum purge channel opening portion are respectively arranged at the tops of the carrier gas channel (7), the coolant channel (10) and the septum purge channel (8), and both of the carrier gas channel opening portion and the septum purge channel opening portion communicate with the opening at the top of the vaporizing chamber (5); the carrier gas channel (7) is provided with a carrier gas inlet (14), the septum purge channel is provided with a septum purge channel outlet (16), and the coolant channel (10) is provided with a coolant inlet (11) and a coolant outlet (17);

    a capillary column (19) is arranged at the bottom of the vaporizing chamber (5), one end of the capillary column (19) projecting into the vaporizing chamber (5), and the other end of the capillary column projecting out of the sample injector;

    a heater (20) is further arranged in the sample injector shell (3),

    said sample injector being characterized in that:

    the heaters (20) are uniformly distributed on the outer wall of the sample injector shell, a temperature control unit (21) is further comprised, and the heaters (20) are controlled by the temperature control unit (21) to achieve single-point temperature heating or programmed temperature heating,

    the inlet of the carrier gas channel (14), the outlet of the septum purge channel (16) and the inlet and the outlet of the coolant channel (10, 17) are all connected with the gas flow control valve (13), and the temperature control unit (21) is further connected with the gas flow control valve (13); the temperature control unit (21) and the gas flow control valve (13) cooperate to cool the sample injector.


     
    2. The sample injector according to claim 1, wherein a inlet liner (6) is fixed in the vaporizing chamber (5), the two ends of the inlet liner (6) are open, the opening at the top of the inlet liner (6) communicates with the opening at the top of the vaporizing chamber (5), and the opening at the bottom of the inlet liner (6) is not in contact with the bottom of the vaporizing chamber (5);
    a gap for enabling the gas to pass is reserved between the outer surface of the inlet liner (6) and the inner surface of the vaporizing chamber (5);
    a ring-shaped sealing and fixing device (4) is arranged at the outer edge of the opening at the top of the inlet liner (6) and at the inner edge of the opening of the vaporizing chamber (5); the inlet liner (6) penetrates through the ring-shaped sealing device (4) to fix the outer edge of the opening at the top of the inlet liner (6) in the vaporizing chamber (5).
     
    3. The sample injector according to claim 2, wherein the sealing ring (4) is made from a high temperature resistant rubber material or a graphite material.
     
    4. The sample injector according to any one of claims 1-3, wherein the sample injector further comprises a flow splitting channel (9), the flow splitting channel (9) is provided with a flow splitting channel opening and a flow splitting channel outlet (15), and the flow splitting channel opening is arranged on the side wall of the vaporizing chamber (5) and communicates with the vaporizing chamber (5).
     
    5. The sample injector according to claim 1, wherein the coolant channel (10) further communicates with the vaporizing chamber (5).
     
    6. The sample injector according to claim 1, wherein a sealing septum (2) is further arranged between the sample injector shell opening and the detachable end cover (1), and a channel for enabling the gas to pass is reserved between the sealing septum (2) and the vaporizing chamber opening.
     
    7. The sample injector according to claim 1, wherein the carrier gas inlet (14), the septum purge channel outlet (16), the coolant inlet (11) and the coolant outlet (17) are all arranged at the bottom of the sample injector shell (3).
     
    8. The sample injector according to claim 1, wherein the sample injector shell (3) is made from a metallic material, and the center of the end cover (1) and the center of the vaporizing chamber (5) are coaxial.
     
    9. The sample injector according to claim 1, wherein the capillary column (19) is arranged just at the central position of the bottom of the vaporizing chamber (5).
     
    10. A gas chromatograph, comprising the sample injector according to any one of claims 1-9.
     
    11. A combined spectrometer, which is a gas chromatography- ion mobility spectrometer and comprises the sample injector according to any one of claims 1-9.
     
    12. A combined spectrometer, which is a gas chromatography-mass spectrometer and comprises the sample injector according to any one of claims 1-9.
     


    Ansprüche

    1. Ein Probeninjektor, aufweisend
    eine Probeninjektor Hülse (3) und eine Verdampfungskammer (5) sich befindend in der Probeninjektor Hülse (3), wobei:

    eine Probeninjektor Hülsen Öffnung und eine lösbare Endabdeckung (1) angeordnet sind an der Oberseite der Probeninjektor Hülse (3) und die Endabdeckung (1) abdichtet die Probeninjektor Hülsen Öffnung;

    eine Verdampfungskammer Öffnung angeordnet ist an der Oberseite der Verdampfungskammer (5) und ein Kanal, um dem Gas ein Passieren zu ermöglichen, freigehalten ist zwischen der Verdampfungskammer Öffnung und der Endabdeckung (1);

    ein Trägergas Kanal (7), ein Septum Spülkanal (8) und ein Kühlmittel Kanal (10) ferner angeordnet sind in der Probeninjektor Hülse (3) entlang des äußeren Umfangs der Verdampfungskammer (5), eine Trägergas Kanal Öffnung Teil und ein Septum Spülkanal Öffnung Teil angeordnet sind auf den Oberseiten des Trägergaskanals (7) respektive des Kühlmittel Kanals (10) und des Septum Spülkanals (8), und sowohl der Trägergas Kanal Öffnung Teil und der Septum Spülkanal Öffnung Teil in Verbindung stehen mit der Öffnung an der Oberseite der Verdampfungskammer (5);

    dem Trägergas Kanal (7) bereitgestellt ist ein Trägergas Einlass (14), dem Septum Spülkanal bereitgestellt ist ein Septum Spülkanal Auslass (16) und dem Kühlmittel Kanal (10) bereitgestellt ist ein Kühlmittel Einlass (11) und ein Kühlmittel Auslass (17);

    eine Kapillarsäule (19) angeordnet ist auf der Unterseite der Verdampfungskammer (5), wobei ein Ende der Kapillarsäule (19) hervorsteht in die Verdampfungskammer (5) und wobei das andere Ende der Kapillarsäule (19) hervorsteht aus dem Probeninjektor heraus;

    ein Erhitzer (20) ferner angeordnet ist in der Probeninjektor Hülse (3), wobei der Probeninjektor dadurch gekennzeichnet ist, dass:

    die Erhitzer (20) gleichmäßig verteilt sind auf der äußeren Wandung der Probeninjektor Hülse, eine Temperatur Steuereinheit (21) ferner aufgewiesen ist, und die Erhitzer (20) gesteuert sind mittels der Temperatur Steuereinheit (21) um zu erreichen ein Einzelpunkt Temperatur Erhitzen oder programmiertes Temperatur Erhitzen,

    der Einlass des Trägergas Kanals (14), der Auslass des Septum Spülkanals (16) und der Einlass und der Auslass des Kühlmittel Kanals (10, 17) alle verbunden sind mit dem Gasfluss Steuerventil (13) und die Temperatur Steuereinheit (21) ferner verbunden ist mit dem Gasfluss Kontrollventil (13);

    die Temperatur Steuereinheit (21) und das Gasfluss Steuerventil (13) zusammenarbeiten zum Kühlen des Probeninjektors.


     
    2. Der Probeninjektor gemäß Anspruch 1, wobei

    ein Einlass Liner (6) fixiert ist in der Verdampfungskammer (5), die zwei Enden des Einlass Liners (6) offen sind, die Öffnung an der Oberseite des Einlass Liners (6) in Verbindung steht mit der Öffnung an der Oberseite der Verdampfungskammer (5) und die Öffnung auf der Unterseite des Einlass Liners (6) nicht in Kontakt steht mit der Unterseite der Verdampfungskammer (5);

    ein Spalt, um dem Gas ein Passieren zu ermöglichen, freigehalten ist zwischen der äußeren Oberfläche des Einlass Liners (6) und der inneren Oberfläche der Verdampfungskammer (5);

    eine ringförmige Abdicht und Fixier Vorrichtung (4) angeordnet ist an der äußeren Kante der Öffnung an der Oberseite des Einlass Liners (6) und an der inneren Kante der Öffnung der Verdampfungskammer (5);

    wobei der Einlass Liner (6) dringt durch die ringförmige Abdicht und Fixier Vorrichtung (4) zum Fixieren der äußeren Kante der Öffnung an der Oberseite des Einlass Liners (6) in der Verdampfungskammer (5).


     
    3. Der Probeninjektor gemäß Anspruch 2, wobei
    der Abdicht Ring (4) gefertigt ist aus einem hochtemperaturbeständigen Gummi Material oder aus einem Graphit Material.
     
    4. Der Probeninjektor gemäß einem der Ansprüche 1 bis 3, wobei der Probeninjektor ferner aufweist einen Fluss Aufteil Kanal (9), wobei dem Fluss Aufteil Kanal (9) bereitgestellt ist eine Fluss Aufteil Kanal Öffnung und ein Fluss Aufteil Kanal Auslass (15) und die Fluss Aufteil Kanal Öffnung angeordnet ist an der seitlichen Wandung der Verdampfungskammer (5) und in Verbindung steht mit der Verdampfungskammer (5).
     
    5. Der Probeninjektor gemäß Anspruch 1, wobei
    der Kühlmittel Kanal (10) ferner in Verbindung steht mit der Verdampfungskammer (5).
     
    6. Der Probeninjektor gemäß Anspruch 1, wobei
    ein Abdicht Septum (2) ferner angeordnet ist zischen der Probeninjektor Hülsen Öffnung und der lösbaren Endabdeckung (1) und ein Kanal, um dem Gas ein Passieren zu ermöglichen, freigehalten ist zwischen dem Abdicht Septum (2) und der Verdampfungskammer Öffnung.
     
    7. Der Probeninjektor gemäß Anspruch 1, wobei
    der Trägergas Einlass (14), der Septum Spülkanal Auslass (14), der Kühlmittel Einlass (11) und der Kühlmittel Auslass (17) alle angeordnet sind auf der Unterseite der Probeninjektor Hülse (3).
     
    8. Der Probeninjektor gemäß Anspruch 1, wobei
    die Probeninjektor Hülse (3) gefertigt ist aus einem metallischen Material, und das Zentrum der Endabdeckung (1) und das Zentrum der Verdampfungskammer (5) koaxial sind.
     
    9. Der Probeninjektor gemäß Anspruch 1, wobei die Kapillarsäule (19) angeordnet ist genau an der zentralen Position der Unterseite der Verdampfungskammer (5).
     
    10. Ein Gaschromatograph, aufweisend
    den Probeninjektor gemäß irgendeinem der Ansprüche 1 bis 9.
     
    11. Ein kombiniertes Spektrometer, welches ein Gaschromatographie Ionenmobilitäts Spektrometer ist und aufweist den Probeninjektor gemäß irgendeinem der Ansprüche 1 bis 9.
     
    12. Ein kombiniertes Spektrometer, welches ein Gaschromatographie Massenspektrometer ist und aufweist den Probeninjektor gemäß irgendeinem der Ansprüche 1 bis 9.
     


    Revendications

    1. Un injecteur d'échantillons, comprenant une coque (3) d'injecteur d'échantillons et une chambre de vaporisation (5) située dans la coque (3) d'injecteur d'échantillons, dans lequel :

    une ouverture de coque d'injecteur d'échantillons et un couvercle d'extrémité (1) séparable sont agencés au sommet de la coque (3) d'injecteur d'échantillons et le couvercle d'extrémité (1) ferme hermétiquement l'ouverture de la coque d'injecteur d'échantillons ;

    une ouverture de chambre de vaporisation est agencée au sommet de la chambre de vaporisation (5), et un canal pour permettre à un gaz de passer est réservé entre l'ouverture de la chambre de vaporisation et le couvercle d'extrémité (1) ;

    un canal (7) de gaz transporteur, un canal (8) de purge de septum et un canal de réfrigérant (10) sont en outre agencés dans la coque (3) d'injecteur d'échantillons le long de la circonférence extérieure de la chambre de vaporisation (5), une partie d'ouverture de canal de gaz transporteur et une partie d'ouverture de canal de purge de septum sont agencées respectivement aux sommets du canal (7) de gaz transporteur, du canal de réfrigérant (10) et du canal (8) de purge de septum, et la partie d'ouverture du canal de gaz transporteur et la partie d'ouverture du canal de purge de septum communiquent toutes deux avec l'ouverture située au sommet de la chambre de vaporisation (5) ; le canal (7) de gaz transporteur est pourvu d'une entrée (14) de gaz transporteur, le canal de purge de septum est pourvu d'une sortie (16) de canal de purge de septum et le canal de réfrigérant (10) est pourvu d'une entrée (11) de réfrigérant et d'une sortie (17) de réfrigérant ;

    une colonne capillaire (19) est agencée au niveau du fond de la chambre de vaporisation (5), une extrémité de la colonne capillaire (19) faisant saillie dans la chambre de vaporisation (5), et l'autre extrémité de la colonne capillaire faisant saillie hors de l'injecteur d'échantillons,

    un élément chauffant (20) est en outre agencé dans la coque (3) d'injecteur d'échantillons,

    ledit injecteur d'échantillons étant caractérisé en ce que :

    les éléments chauffants (20) sont répartis uniformément sur la paroi extérieure de la coque d'injecteur d'échantillons, une unité (21) de contrôle de température est en outre comprise, et les éléments chauffants (20) sont commandés par l'unité (21) de contrôle de température de façon à obtenir un chauffage à point unique de température ou un chauffage à une température programmée,

    l'entrée (14) du canal de gaz transporteur, la sortie (16) du canal de purge de septum et l'entrée et la sortie (10, 17) du canal de réfrigérant sont toutes connectées à la vanne (13) de commande d'écoulement de gaz, et l'unité (21) de contrôle de température est en outre connectée à la vanne (13) de commande d'écoulement de gaz ; l'unité (21) de contrôle de température et la vanne (13) de commande d'écoulement de gaz coopèrent pour refroidir l'injecteur d'échantillons.


     
    2. L'injecteur d'échantillons selon la revendication 1, dans lequel un chemisage d'entrée (6) est fixé dans la chambre de vaporisation (5), les deux extrémités du chemisage d'entrée (6) sont ouvertes, l'ouverture située au niveau du sommet du chemisage d'entrée (6) communique avec l'ouverture située au niveau du sommet de la chambre de vaporisation (5), et l'ouverture située au niveau de la partie inférieure du chemisage d'entrée (6) n'est pas en contact avec le fond de la chambre de vaporisation (5) ;
    un espace pour permettre au gaz de passer est réservé entre la surface extérieure du chemisage d'entrée (6) et la surface intérieure de la chambre de vaporisation (5) ; un dispositif (4) en forme d'anneau, d'étanchéité et de fixation, est agencé sur le bord extérieur de l'ouverture au niveau du sommet du chemisage d'entrée (6) et sur le bord intérieur de l'ouverture de la chambre de vaporisation (5) ;
    le chemisage d'entrée (6) pénètre à travers le dispositif d'étanchéité (4) en forme d'anneau pour fixer le bord extérieur de l'ouverture située au niveau du sommet du chemisage d'entrée (6) dans la chambre de vaporisation (5).
     
    3. L'injecteur d'échantillons selon la revendication 2, dans lequel l'anneau d'étanchéité (4) est constitué d'un matériau en caoutchouc résistant aux hautes températures ou d'un matériau en graphite.
     
    4. L'injecteur d'échantillons selon l'une quelconque des revendications 1 à 3, dans lequel l'injecteur d'échantillons comprend en outre un canal (9) de séparation d'écoulement, le canal (9) de séparation d'écoulement est pourvu d'une ouverture de canal de séparation d'écoulement et d'une sortie (15) canal de séparation d'écoulement, et l'ouverture du canal de séparation du débit est agencée sur la paroi latérale de la chambre de vaporisation (5) et communique avec la chambre de vaporisation (5).
     
    5. L'injecteur d'échantillons selon la revendication 1, dans lequel le canal de réfrigérant (10) communique en outre avec la chambre de vaporisation (5).
     
    6. L'injecteur d'échantillons selon la revendication 1, dans lequel un septum d'étanchéité (2) est en outre agencé entre l'ouverture de la coque de l'injecteur d'échantillons et le couvercle d'extrémité (1) séparable, et un canal pour permettre au gaz de passer est réservé entre le septum d'étanchéité (2) et l'ouverture de la chambre de vaporisation.
     
    7. L'injecteur d'échantillons selon la revendication 1, dans lequel l'entrée (14) de gaz transporteur, la sortie (16) du canal de purge de septum, l'entrée (11) de réfrigérant et la sortie (17) de réfrigérant sont toutes agencées au niveau de la partie inférieure de la coque de l'injecteur d'échantillons (3).
     
    8. L'injecteur d'échantillons selon la revendication 1, dans lequel la coque (3) d'injecteur d'échantillons est faite en un matériau métallique, et le centre du couvercle d'extrémité (1) et le centre de la chambre de vaporisation (5) sont coaxiaux.
     
    9. L'injecteur d'échantillons selon la revendication 1, dans lequel la colonne capillaire (19) est agencée juste à la position centrale du fond de la chambre de vaporisation (5).
     
    10. Un chromatographe à gaz, comprenant l'injecteur d'échantillons selon l'une quelconque des revendications 1 à 9.
     
    11. Un spectromètre combiné, qui est un spectromètre à chromatographie en phase gazeuse et à mobilité ionique et qui comprend l'injecteur d'échantillons selon l'une quelconque des revendications 1 à 9.
     
    12. Un spectromètre combiné, qui est un spectromètre de chromatographie en phase gazeuse et de masse et qui comprend l'injecteur d'échantillons selon l'une quelconque des revendications 1 à 9.
     




    Drawing








    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description




    Non-patent literature cited in the description