US3827859A - Flame ionization detector for supercritical fluid chromatography - Google Patents

Flame ionization detector for supercritical fluid chromatography Download PDF

Info

Publication number
US3827859A
US3827859A US00310166A US31016672A US3827859A US 3827859 A US3827859 A US 3827859A US 00310166 A US00310166 A US 00310166A US 31016672 A US31016672 A US 31016672A US 3827859 A US3827859 A US 3827859A
Authority
US
United States
Prior art keywords
flame ionization
ionization detector
separating column
supercritical fluid
burner nozzle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00310166A
Other languages
English (en)
Inventor
O Vitzthum
P Hubert
M Barthels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hag AG
Original Assignee
Hag AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hag AG filed Critical Hag AG
Application granted granted Critical
Publication of US3827859A publication Critical patent/US3827859A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G01N30/68—Flame ionisation detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y10T436/142222—Hetero-O [e.g., ascorbic acid, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/200833—Carbonyl, ether, aldehyde or ketone containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/203332—Hydroxyl containing

Definitions

  • a flame ionization detector for use with supercritical fluid chromatography apparatus wherein the reducing valve which transforms the test gas coming from the separating column under supercritical conditions to subcritical conditions before burning at the burner nozzle, is in the form of one or more diaphragms disposed immediately upstream of the burner nozzle outlet and having central bores whose diameters are in the range from 2 to microns.
  • the present invention relates to a flame ionization detector for use in supercritical fluid chromatography.
  • the pressure and the temperature of the supercritical carrier gas which contains the high molecular substances in dissolved form, are generally reduced by means of a reducing valve, usually in the form of a needle valve, to subcritical conditions through expansion. This is described more fully in chemie-Ingenieur-Technik, 42 (1970), p. 703, FIG. 1.
  • the supercritical carrier gas is expanded to subcritical conditions directly upstream of the burner nozzle of the flame ionization detector by reducing the pressure with a diaphragm arrangement provided With a fine central bore positioned a short distance upstream of the burner nozzle.
  • the diameter of the central bore of a suitable diaphragm in accordance with the present invention may be in the range from 2 to 10 microns, e.g. 2.5 5 or 10,44. Such bores can be produced, for example, with a power laser.
  • One or several such diaphragms may be installed, depending upon the operating pressure used in the separating column of the fluid chromatographic system.
  • the outflow velocity of CO with an inlet pressure of 250 atm. is limited to 70 ml./min., an amount which does not overload the flame ionization detector.
  • four diaphragms of 0.2 mm To achieve a similar reduction of the outflow velocity with an inlet pressure of 1000 atm.
  • the diaphragms may be of a thickness of about 0.1 mm. or 0.2 mm. and consist preferably of platinum-iridium.
  • the flame ionization detector is constantly heated with a 50 watt heater.
  • FIG. 1 is a schematic showing of a supercritical fluid chromatography system.
  • FIG. 2 is a sectional view of a flame ionization detector in accordance with the present invention.
  • FIGS. 3-7 are chromatograms obtained in the tests described in examples 1-5, respectively.
  • FIG. 1 A supercritical fluid chromatographic system with which the present invention may be used is shown in FIG. 1.
  • Pressure bottle 1 contains a supply of CO carrier gas and feeds this gas through a cleaning column 2, a heat-exchanger 3 for heating the CO and a two-stage diaphragm compressor 4. The latter two components are bridged by a bypass valve 5 and feed the carrier gas into a temperable waterbath 12 containing the separating column system.
  • This system contains a throttle valve 6, a buffer autoclave 7, a heat exchanger 8 and an injection block 9.
  • the separating column itself, 11, has manometers 10 and 13 disposed at either side to indicate the pressure in the inlet line and the outlet line respectively.
  • the outlet line is connected to a flame ionization detector 15 and also to a split valve 14.
  • a flame ionization detector 15 in accordance with the present invention is shown in detail in FIG. 2.
  • a detector housing 16 is inserted a heated burner nozzle 17 which may be made of a thick walled 4571-VA steel.
  • Hydrogen is supplied through a capillary tube 18 into the nozzle duct 17a while a fuel gas such as synthetic air, is fed through tube 24 into the burner chamber 16a.
  • An ignition electrode 26 is provided for initiating burning and the waste gases issued from the chamber 16a through opening in the housing 16 wall.
  • the carrier gas issuing from the separating column 11 of the chromatographic system under high pressure conditions is fed together with the dissolved substances to the flame ionization detector 15 through a pipe element 20 containing capillary tube 19.
  • a pipe element 20 containing capillary tube 19 At the transition point between the pipe 20 and the nozzle duct 17a is disposed the diaphragm arrangement of the present invention.
  • the arrangement comprises a thin diaphragm 21 supported just upstream of the nozzle duct 17a by a stitfening piece 23 and with a gold packing 22 on its upstream side for sealing the high-pressure chamber within pipe 20.
  • the high pressure gas is expanded through bore 21a in diaphragm 21 to normal pressure upon entering the nozzle duct 17a.
  • the arrangement may be adapted for various pressure gradients by varying the size of the bore 21a in the diaphragm 21 which as previously stated may be in the range from 2 to 10 microns, and/or by using a stack of several diaphragms 21, each with an interposed packing 22.
  • EXAMPLE 1 The flame ionization detector was used in the detection of 2,4-climethyl phenol.
  • test 1 ul. (microliter) of a mixture of 2,4-dimethyl phenol (2) and 50% benzene (1) was used.
  • Diameter of separating column 2 mm. Length of separating column: 3 In. Filling of separating column: Durapak/Carbowax 400/ Porasil C, 100/120 mesh Working conditions:
  • Carrier gas CO Pressure in the separating column: 155 kg./cm.
  • the flow ratio for the FID is 1:10, so that about 200 ml./min. pass through the FID.
  • Diameter of separating column 2 mm. Length of separating column: 3 m. Filling of separating column Durapak/Carbowax 400/ Porasil C, /120 mesh Working conditions:
  • Carrier gas CO Pressure in separating column: 300 kg./cm. Temperature in separating column: 60 C. Outflow velocity for separating column: 4 l./min.
  • the flow ratio for the FID is 1:20, so that about 200 ml./min. pass through the FID.
  • Diameter of separating column 2 mm. Length of separating column: 3 m. Filling of separting column: Durapak/Carbowak 400/ Porisil C, 100/ mesh Working conditions:
  • Carrier gas CO Pressure in separting column: 244 kg./cm. Temperature in separating column: 40 C. Outflow velocity from separating column: 1 l./min.
  • the flow ratio for the FID is 1:10, so that about 100 ml./min. pass through the FID.
  • Outflow velocity for the FID is 1:20, so that about 200 mL/min. pass through the FID.
  • EXAMPLE 5 Separation of a mixture of aromatic substances: For the test is used 1 ,ul. (microliter) of a mixture of benzene, toluene, xylene, naphthalene, fluorene and phenanthrene.
  • Carrier gas CO Pressure in separating column: 75200 kg/cm. Temperature in separating column: 40 C. Diameter of aperture in the FIB-diaphragm: g Flow velocity through the FID-diaphragm: 40100 ml./min.
  • the diaphragm 21 be disposed upstream of the burner nozzle a distance of less than 10 mm. and preferably within the range from 4 to 6 mm. from the nozzle exit.
  • Wlnat is claimed is:
  • Flame ionization detector particularly for use in supercritical fluid chromatography apparatus of the type having:
  • said reducing means comprises: (e) at least one diaphragm disposed upstream of said burner nozzle outlet duct and having a bore through which test gas passes, whose diameter is in the range from 2 to 10 microns.
  • a detector as in claim 1 wherein the diaphragm is of platinum-iridium.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
US00310166A 1971-11-30 1972-11-28 Flame ionization detector for supercritical fluid chromatography Expired - Lifetime US3827859A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2159339A DE2159339C3 (de) 1971-11-30 1971-11-30 Flammenionisationsdetektor (FID) für die überkritische Fluidchromatographie

Publications (1)

Publication Number Publication Date
US3827859A true US3827859A (en) 1974-08-06

Family

ID=5826591

Family Applications (1)

Application Number Title Priority Date Filing Date
US00310166A Expired - Lifetime US3827859A (en) 1971-11-30 1972-11-28 Flame ionization detector for supercritical fluid chromatography

Country Status (7)

Country Link
US (1) US3827859A (it)
CH (1) CH548602A (it)
DE (1) DE2159339C3 (it)
FR (1) FR2163118A5 (it)
GB (1) GB1354208A (it)
IT (1) IT971038B (it)
NL (1) NL7215530A (it)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4346055A (en) * 1978-11-29 1982-08-24 Hewlett-Packard Company Automatic ignition system for a flame ionization detector
US5205987A (en) * 1991-02-28 1993-04-27 Suprex Corporation Off-line supercritical fluid extraction collection system
US20220276208A1 (en) * 2019-01-14 2022-09-01 Agilent Technologies, Inc. Versatile tube-free jet for gas chromatography detector

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4346055A (en) * 1978-11-29 1982-08-24 Hewlett-Packard Company Automatic ignition system for a flame ionization detector
US5205987A (en) * 1991-02-28 1993-04-27 Suprex Corporation Off-line supercritical fluid extraction collection system
US20220276208A1 (en) * 2019-01-14 2022-09-01 Agilent Technologies, Inc. Versatile tube-free jet for gas chromatography detector
US12117424B2 (en) 2019-01-14 2024-10-15 Agilent Technologies, Inc. Versatile tube-free jet for gas chromatography detector having a conical inlet skirt
US12130266B2 (en) * 2019-01-14 2024-10-29 Agilent Technologies, Inc Versatile tube-free jet for gas chromatography detector having a conical inlet skirt

Also Published As

Publication number Publication date
IT971038B (it) 1974-04-30
GB1354208A (en) 1974-06-05
DE2159339B2 (de) 1975-03-27
CH548602A (de) 1974-04-30
NL7215530A (it) 1973-06-04
DE2159339C3 (de) 1975-11-13
FR2163118A5 (it) 1973-07-20
DE2159339A1 (de) 1973-06-14

Similar Documents

Publication Publication Date Title
US4814089A (en) Chromatographic separation method and associated apparatus
US4871453A (en) Chromatographic separation method and associated apparatus
US4980057A (en) Apparatus for mass spectrometric analysis of liquid chromatographic fractions
US4444040A (en) Method and apparatus for detecting gas components in oil in oil-filled device
EP0088439B1 (en) Gas chromatographic apparatus
US3638396A (en) Gas chromatograph interfacing system and method
Huber et al. Reduction of theoretical plate height in gas chromatography by increase of pressure and decrease of particle size
US3589869A (en) Chemical-ionization detection method and apparatus
Kientz et al. On-line flame photometric detection in micro-column liquid chromatography
GB1500631A (en) Chromatographic analysis of machine coolant
GB1512123A (en) Detection of specific compounds using a liquid chromatograph
Ligon et al. Particle beam interface for liquid chromatography/mass spectrometry
US3677709A (en) Flame ionization detection apparatus and method
Issenberg et al. Combined gas chromatography-mass spectrometry in flavor research. Methods and applications
US3967931A (en) Flame aerosol detector for liquid chromatography
US3656339A (en) Glow discharge detector
Matsumoto et al. Fundamental conditions in pressure-programmed supercritical fluid chromatography-mass spectrometry and some applications to vitamin analysis
WO1996006349A1 (en) Improved flame ionization detector
Abdel‐Rehim et al. Capillary gas chromatography of amines with ammonia as carrier gas
Compton et al. Phosphorus-sensitive detectors for high-performance liquid chromatography I. Modification of A transport flame ionization detector to the thermal ionic detector mode
Boček et al. Effect of pressure on the performance of the flame ionization detector
Van Ysacker et al. Electron caputure detection in high‐speed narrow‐bore capillary gas chromatography: Fast and sensitive analysis of PCBs and pesticides
Flett et al. The application of a long-path infra-red cell in gas chromatography
DE2159339C3 (de) Flammenionisationsdetektor (FID) für die überkritische Fluidchromatographie
Bernier et al. Vacuum operation of the flame-ionization detector for gas chromatography