CN1623088A - Chemical substance detector and method for detecting chemical substance - Google Patents

Chemical substance detector and method for detecting chemical substance Download PDF

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Publication number
CN1623088A
CN1623088A CN03801491.2A CN03801491A CN1623088A CN 1623088 A CN1623088 A CN 1623088A CN 03801491 A CN03801491 A CN 03801491A CN 1623088 A CN1623088 A CN 1623088A
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chemical substance
detected object
mentioned
ion
object chemical
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CN100458435C (en
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山越英男
二见博
团野实
鹤我薰典
栗林志头真
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/426—Methods for controlling ions
    • H01J49/427—Ejection and selection methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/162—Direct photo-ionisation, e.g. single photon or multi-photon ionisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The invented detecting device (100) for chemical matter is equipped with a vacuum UV lamp (3), which is used to ionize the to-be-detected target chemical matter in the exhaust Gs. The ionized to-be-detected target chemical matter is isolated by an ion capture device (10) with high frequency electric field formed therein. The ion group in the ion capture device (10) is provided with energy by SWIFT waveform (which comprises frequency component excluding the frequency corresponding to the orbit resonance frequency of the to-be-detected target chemical matter ion) and impurities are removed. Furthermore, the above-mentioned ion group is provided with energy by TICKLE waveform (which comprises frequency component corresponding to the orbit resonance frequency of the to-be-detected target chemical matter ion) and the to-be-detected target chemical matter ion is segmented. Therefore, the mass of the segment is determined by a mass analyzer (4) to identify the to-be-detected target chemical matter.

Description

The pick-up unit of chemical substance and the detection method of chemical substance
Technical field
The present invention relates to a kind of pick-up unit of chemical substance and the method for measurement of concentration of chemical substance, particularly relate to pinpoint accuracy and detect the pick-up unit of the chemical substance that denier dioxin contained in the exhaust of waste incineration facility or its precursor use and the detection method of chemical substance.
Background technology
In recent years,, measure dioxin contained in the exhaust or its precursor immediately for reducing contained dioxin from the exhaust that the waste incineration facility is discharged, and among the test that is used for the burning control of incinerator studying.In the mensuration of dioxin, though the known assay method that has by the GC/MS (gas chromatography/mass analyzer) of high de-agglomeration ability, this method needs complicated pre-treatment, at present from taking sample to need time several weeks till result of determination.Therefore, be difficult to be applicable to instant control as above-mentioned.Be head it off, once disclose by atmospheric pressure chemical ionization method dioxin contained in the exhaust or its precursor ionization, again with three-dimensional four utmost point mass analyzers measure its ion at thread detector.In addition, relevant should research presentations in the 11st time discarded object association and give a lecture the detailed description that put down in writing it in the collection of thesis 2000 at thread detector can give reference if needed.
In addition, above-mentioned atmospheric pressure chemical ionization method has following problem points.At first, because its instrumentation principle, it is low that instrumentation is difficult to form the sensitivity of molecule of negative ion, is difficult to be applicable to accurate control.In addition, the ionization accuracy rate of instrumentation object chemical substance is subjected to the influence of atmosphere gas composition deeply.Therefore, for from being calculated its concentration by the electrical signal intensity of instrumentation, be necessary to use the isotopic chemical substance of C that contains high price as the internal standard test portion, required cost uprises when therefore measuring.
Secondly, above-mentioned atmospheric pressure chemical ionization method is relevant with the concentration of dioxin, and is generally the situation that the higher phenols of instrumentation remolding sensitivity is detected.Yet because phenols easily is attached on the pipe arrangement, memory (memory) effect is very big, if piping work is not careful, can't measure with excellent sensitivity.In addition, because this memory effect, even exhaust is very clean, the detected mensuration degree of accuracy of phenols also reduces.In addition, if be present in the exhaust than the easier Ionized material of the precursor that will survey, these will be ionized earlier, thereby make the material that must measure be difficult to correctly be measured.
In addition, even in a certain stove, have a certain precursor (for example trichlorophenol) can be as the suitableeest index substance of dioxin concentration, but in other stoves, the suitableeest index substance will be with the kind of stove and burning condition etc. and is different.Therefore, in other stoves, the index substance of above-mentioned stove might not be for the suitableeest, if can only precursor of instrumentation then versatility will reduce.Also promptly, for improving versatility, be preferable with the method that various different types of chemical substances can be detected simultaneously.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of pick-up unit of chemical substance and the detection method of chemical substance, it can reach in the following function one at least: the detection sensitivity of detected object chemical substance is improved; When even incinerator, heating furnace or the running of other combustion furnaces are the most prosperous, the detection speed of detected object chemical substance are improved, and make the checkout equipment cost degradation.
The pick-up unit of chemical substance of the present invention, it is characterized by and possess: will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance; By electric field, magnetic field and other mechanisms, will contain ion trap mechanism with the ion swarm sealing of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion; Offer above-mentioned ion swarm energy to remove the impurity removing mechanism of impurity by SWIFT waveform (it comprises the frequency content after the frequency eliminating corresponding with the orbit resonance frequency of this detected object chemical substance ion); And the quality analysis mechanism that measures the quality of above-mentioned detected object chemical substance.
In addition, the pick-up unit of this chemical substance, be when the ionization of detected object chemical substance, will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance.Therefore, owing to can not destroy under the detected object chemical substance its ionization, thereby can improve Ionization Efficiency.
In addition, only give the SWIFT waveform when removing impurity, can remove impurity apace.In addition, in ionization of the present invention,, can or not dissociate or ionization incoherent various molecules because the required energy of ionization is suitably set.Therefore, the generation of fragment is considerably less, and in choosing deimpurity process, it is few that the impurity that must remove also becomes.As a result owing to SWIFT voltage can be forced down, do not destroy should be residual the detected object chemical substance under finish the removal of impurity, the detection sensitivity of the analysis institution of therefore can improving the quality.In addition, need not to prepare excessive power supply, can force down the manufacturing cost of device.In addition, the pick-up unit of chemical substance of the present invention can be extremely minimum with the generation compacting of unnecessary fragment.Therefore, the capture rate reduction that a large amount of existence of ion trap device internal cause excess ions can be caused is suppressed to minimum.Herein, in the quality analysis mechanism,, be preferable especially can shorten the instrumentation time if use flight time instrumentation mode.In addition, in the ion trap mechanism, can use by electric field, magnetic field or other electromagnetism strength ion is closed in inner device.Use separately can be distinguished in electric field and magnetic field, also a plurality of the combination aptly can be used.The ion trap mechanism of this kind mode, known have the ion trap device that forms high-frequency electric field in inside, because it is than being easier to operation, so be preferable (following identical).
In addition, term among the present invention " detected object chemical substance " is meant the dioxin precursor that contained in for example exhaust such as incinerator or dioxin etc.This kind situation, the pick-up unit of chemical substance of the present invention can detect the precursor with the dioxin height correlation, infers contained dioxin concentration in the exhaust.In addition, also can directly detect dioxin contained in the exhaust, try to achieve its concentration simultaneously.The latter also can use when checking the guess value that produces based on precursor.Herein, dioxin is meant the molecule that refers to comprise general dioxin, furans or be called as coplane PCB.In addition, for example comprise phenols such as benzene class such as trichloro-benzenes, dichloro-benzenes and chlorobenzene or trichlorophenol in the precursor.
In addition, " SWIFT " is meant " storing the conversion of waveform inverse-Fourier " (" Stored WaveformInverse Fourier Transform "), its detailed description, but list of references " Development of aCapillary High-perfOrmance Liquid Chromatography Tandem MassSpectrometry System Using SWIFT Technology in an Ion Trap/ReflectronTime-of-flight Mass Spectrometer " Rapid Communication in MassSpectrometry, vol.11,1739-1748 (1997).
In addition, the pick-up unit of chemical substance of the present invention, it is characterized by and possess: will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance; By electric field, magnetic field and other mechanisms, will contain ion trap mechanism by the ion swarm sealing of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion; Offer above-mentioned ion swarm energy to remove the impurity removing mechanism of impurity by SWIFT waveform (it comprises the frequency content that the frequency corresponding with the orbit resonance frequency of above-mentioned detected object chemical substance ion got rid of); Offer above-mentioned ion swarm energy by TICKLE waveform (its for the corresponding frequency content of orbit resonance frequency of detected object chemical substance ion), so that the fragmentation mechanism of the fragment ionization of detected object chemical substance; And the quality analysis mechanism that measures the quality of above-mentioned detected object chemical substance fragment.
In the pick-up unit of this chemical substance,, and correctly measure because its influence with detected object chemical substance fragmentation, even therefore in the mass number of detected object chemical substance impurity is arranged, also can be got rid of by the fragmentation mechanism by offering the TICKLE waveform.In addition, because the fragment that produces during ionization is few, therefore under situation, can the detected object chemical substance of object fragmentation efficiently will be with detected object chemical substance fragmentation.As a result, because almost all the fragment of detected object chemical substance all can be as the determination object of quality analysis mechanism, the detection sensitivity of the analysis institution of therefore can improving the quality, and the control of can more critically burning.Herein, TICKLE instigates detected object chemical substance fragmentation, with the operation that will separate with the detected object chemical substance with the impurity that detected object chemical substance mass number is similar to, its detailed description can be with reference to above-mentioned document " Development of aCapillary High-performance Liquid Chromatography Tandem MassSpectrometry System Using SWIFT Technology in an Ion Trap/ReflectronTime-of-flight Mass Spectrometer ".
In addition, being characterized as of the pick-up unit of chemical substance of the present invention, in the pick-up unit of above-mentioned chemical substance, above-mentioned ionization mechanism will be for offering above-mentioned detected object chemical substance than ionization potential height and the energy below the value that adds 4eV on this ionization potential.Secondly, being characterized as of the pick-up unit of chemical substance of the present invention, in the pick-up unit of above-mentioned chemical substance, above-mentioned ionization mechanism is for producing the light generation mechanism of the following light of the above 200nm of wavelength 50nm.In addition, being characterized as of the pick-up unit of chemical substance of the present invention, in the pick-up unit of above-mentioned chemical substance, above-mentioned ionization mechanism is the vacuum ultraviolet light modulation.
As described in these inventions, when energy is provided in ionization mechanism to the detected object chemical substance, this energy with and the value following person that on this ionization potential add 4eV higher than ionization potential for preferable.In addition, during with the ionization of detected object chemical substance, be preferable at the energy by light with the light below the above 200nm of wavelength 50nm.In addition, if these light use the vacuum ultraviolet light modulation, so owing to can easily obtain preferable.
In addition, the pick-up unit of chemical substance of the present invention is characterized by and possesses: the ion trap mechanism that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; The random waveform that produces the SWIFT waveform produces mechanism, wherein the voltage amplitude that has in the pairing frequency of orbit resonance frequency of the impurity that the concentration that is higher than the signal intensity that sets signal intensity with demonstration exists of this SWIFT waveform is bigger than the voltage amplitude in the pairing frequency band of orbit resonance frequency of the impurity that exists in the concentration that is lower than the signal intensity that sets signal intensity with demonstration; And will produce the above-mentioned SWIFT waveform that mechanism generated by this random waveform, offer the ion swarm that in above-mentioned ion trap mechanism, is closed with after removing above-mentioned impurity, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
Among the present invention, owing to will improve with voltage amplitude than the SWIFT waveform that sets the impurity mass number institute respective frequencies that the high concentration of signal intensity exists, and the voltage amplitude of the mass number that impurity concentration is low institute respective frequencies reduces, and therefore can optionally remove the impurity of high concentration especially.Therefore, owing to can optionally remove impurity, the SWIFT energy needed can be finished less.In addition, owing to the supply unit miniaturization can be need not to use excessive power supply, therefore comparatively economical., improve the impurity of the voltage amplitude of SWIFT waveform herein, the impurity of preferred object for existing with identical with the signal intensity of the detected object chemical substance at least concentration of signal intensity.In addition, though also can be little the impurity that exists of mass number be object, yet if so because the SWIFT energy needed becomes big, so be object preferably with the impurity of the signal intensities of signal intensity more than 5 one-tenth with detected object chemical substance.
In addition, the pick-up unit of chemical substance of the present invention is characterized by and possesses: the ion trap mechanism that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; Generation is along with frequency becomes big and the random waveform generation mechanism SWIFT waveform that voltage amplitude dwindles; And above-mentioned SWIFT waveform offered the ion swarm that is closed with after removing above-mentioned impurity in above-mentioned ion trap mechanism, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
The pick-up unit of this chemical substance of the present invention, the impurity big for mass number provides and offers the energy of the energy same degree of the little impurity of mass number.Generally speaking, the orbit resonance frequency in the ion trap is the function of mass number, and mass number is big more, and then frequency is more little, and the frequency interval that is equivalent to mass number interval 1 becomes narrow and small.On the other hand, at document " Development of aCapillary High-performance Liquid Chromatography Tandem MassSpectrometry System Using SWIFT Technology in an Ion Trap/ReflectronTime-of-flight Mass Spectrometer " in the past, Rapid Communication in MassSpectrometry, vol.11, the generation of the SWIFT waveform that generally carries out among the 1739-1748 (1997) etc., carry out anti-Fourier (Fourier) conversion by the frequency spectrum that voltage amplitude is constant, and the conversion time field generates the SWIFT waveform.This kind situation with constant frequency interval, generates the waveform with constant voltage amplitude shape sum.Thereby, this kind situation, because mass number is big more, the sinusoidal undulation number at average quality number interval 1 is few, average quality number 1 energy at interval also lacks.That is, the energy that is added on the big molecule of mass number relatively diminishes.
Therewith relatively, because the present invention's sine voltage amplitude that sinusoidal undulation number is few increases revisal, the ion big for mass number also can provide sufficient energy, therefore this kind impurity more positively can be removed.In addition, in the little ion of mass number,, can improve the service efficiency of energy owing to can in needed abundant scope, provide its energy.In addition, because of not needing excessive supply unit, but also reducing apparatus cost is set.
In addition, the pick-up unit of chemical substance of the present invention is characterized by and possesses: the ion trap mechanism that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; No matter the mass number size of the subject molecule of removing by SWIFT, the random waveform that produces the SWIFT waveform with the constant distribution of voltage amplitude produces mechanism; And above-mentioned SWIFT waveform offered the ion swarm that is closed with after removing above-mentioned impurity in above-mentioned ion trap mechanism, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
The pick-up unit of this chemical substance will diminish and the frequency spectrum of the big SWIFT waveform of voltage amplitude amplitude variation along with frequency, when making mass number regard the transverse axis conversion, and the rough steady state value that becomes of voltage amplitude of average unit mass number.Therefore, to the molecule of any quality of the object removed by SWIFT, all can give rough constant energy.Thus, the ion big for mass number also can provide sufficient energy, this kind impurity more positively can be removed.In addition, at the little ions of mass number,, can improve the service efficiency of energy owing to can in needed abundant scope, provide its energy.In addition, because of not needing excessive supply unit, but also reducing apparatus cost is set.
In addition, the pick-up unit of chemical substance of the present invention is characterized by and possesses: will contain ion trap mechanism by the ion swarm sealing of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion by electric field, magnetic field and other mechanisms; The random waveform that produces the SWIFT waveform produces mechanism, and wherein this SWIFT waveform is not given voltage amplitude in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances, and gives voltage amplitude in the frequency band corresponding to the mass number of impurity; Energy is provided for above-mentioned ion swarm by TICKLE waveform (it has a plurality of frequency contents corresponding to the orbit resonance frequency of above-mentioned a plurality of detected object chemical substances), so that the fragmentation mechanism of the fragment ionization of described a plurality of detected object chemical substances; And above-mentioned SWIFT waveform offered the ion swarm that is closed with after removing above-mentioned impurity in above-mentioned ion trap mechanism, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
Because it is contained dioxin and precursor denier thereof in the exhaust of incinerator improves their detection degree of accuracy, very important in the instant situation about controlling of the burning condition of incinerator.The pick-up unit of chemical substance of the present invention, using does not provide the SWIFT waveform of voltage amplitude to remove impurity in corresponding to the frequency band of a plurality of detected object chemical substances.Then, a plurality of detected object chemical substances are detected simultaneously by quality analysis mechanism.Like this,, can carry out the high mensuration of degree of accuracy, also can improve the degree of accuracy of burning control because a plurality of detected object chemical substances are detected simultaneously.
In addition, the pick-up unit of chemical substance of the present invention, it is characterized by, in the pick-up unit of above-mentioned chemical substance, other possesses bigger than the ionization potential of detected object chemical substance and littler than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum energy is offered this detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance.In addition, being characterized as of the pick-up unit of chemical substance of the present invention, in the pick-up unit of above-mentioned chemical substance, above-mentioned ionization will offer above-mentioned detected object chemical substance than ionization potential height and the energy below the value that adds 4eV on this ionization potential in section.
The pick-up unit of the chemical substance of these inventions will offer this detected object chemical substance than the ionization potential height and the energy littler than dissociation energy of detected object chemical substance, with this detected object chemical substance ionization.Therefore, can not generate unnecessary fragment, under the situation of not destroying detected object chemical substance that should be residual, finish the detection sensitivity of the analysis institution of can improving the quality.Therefore, the effect and the effect that produce with above-mentioned chemical substance pick-up unit complement each other, and the detection sensitivity of quality analysis mechanism is improved, but the degree of accuracy highland are measured.Then, in the burning control of incinerator, can more compactly control.In addition,, need not to prepare excessive power supply, can reduce the manufacturing cost of device owing to can reduce SWIFT voltage.
The detection method of chemical substance of the present invention, it is characterized by and have: will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance; By electric field, magnetic field and other mechanisms, will contain the ion trap step of the ion swarm sealing of Ionized detected object chemical substance ion; Provide energy to remove step for above-mentioned ion swarm by SWIFT waveform (it comprises the frequency content that the frequency corresponding with the orbit resonance frequency of above-mentioned detected object chemical substance ion got rid of) with the impurity of removing impurity: and the quality analysis step of the quality of the above-mentioned detected object chemical substance of mensuration.
The detection method of this chemical substance when removing impurity, will offer this detected object chemical substance than the ionization potential height and the energy littler than dissociation energy of detected object chemical substance.Therefore, can not destroy the detected object chemical substance and remove impurity, in addition, when removing impurity, the generation of unnecessary fragment is few.Therefore, do not destroy should be residual the detected object chemical substance under finish the detection sensitivity of the analysis institution of can improving the quality.In addition, owing to only give SWIFT waveform, can remove impurity apace when removing impurity.In addition,, need not to prepare excessive power supply, can reduce the manufacturing cost of device owing to can force down SWIFT voltage.
In addition, the detection method of chemical substance of the present invention, it is characterized by and have: will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance; By electric field, magnetic field and other mechanisms, the ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion:, provide energy to remove step for above-mentioned ion swarm with the impurity of removing impurity by SWIFT waveform (it comprises the frequency content that the frequency corresponding with the orbit resonance frequency of above-mentioned detected object chemical substance ion got rid of); By TICKLE waveform (it is the frequency content corresponding to the orbit resonance frequency of detected object chemical substance ion), provide energy so that the fragmentation step of the fragment ionization of detected object chemical substance for above-mentioned ion swarm: and the quality analysis step of the quality of the above-mentioned detected object chemical substance fragment of mensuration.
The detection method of this chemical substance by providing the TICKLE waveform to the detected object chemical substance, with detected object chemical substance fragmentation, even have impurity corresponding to the frequency of the mass number of detected object chemical substance, also can be got rid of its influence, correctly measures.In addition, because the fragment that takes place during ionization is few, under situation with detected object chemical substance fragmentation, can be with purpose detected object chemical substance fragmentation efficiently.As a result, since almost all the fragment of detected object chemical substances all can in the quality analysis step, can improve the detection sensitivity of analysis as the object of quality analysis.By this detection method, when the burning condition of control incinerator, the control of can more critically burning.
In addition, the detection method of chemical substance of the present invention is characterized by and has: the ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; Measure the distribution of above-mentioned ion swarm impurities, SWIFT waveform (it comprises the impurity corresponding frequency content above with there being the regulation ratio) is offered above-mentioned ion swarm remove step with the impurity of removing impurity; And the quality analysis step of measuring the quality of above-mentioned detected object chemical substance or its fragment.
The detection method of this chemical substance can optionally be removed the impurity that exists with the amount more than the preset proportion.Therefore, compare with the situation of removing all impurity, available a little energy can be removed the very necessary impurity of removing.Therefore, can be with the supply unit miniaturization, comparatively economical.Herein, the ratio of setting, being preferably is object with the signal intensity impurity identical or above with the signal intensity of detected object chemical substance at least.In addition, though can the little impurity of signal intensity be object also, yet if so, because the SWIFT energy needed becomes big, so preferable impurity with the signal intensities of signal intensity more than 5 one-tenth with above-mentioned detected object chemical substance is object.
In addition, the detection method of chemical substance of the present invention is characterized by and has: the ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; The SWIFT waveform is offered above-mentioned ion swarm remove step with the impurity of removing impurity, wherein the voltage amplitude that has in the pairing frequency of orbit resonance frequency of the impurity that the concentration that is higher than the signal intensity that sets signal intensity with demonstration exists of this SWIFT waveform is bigger than the voltage amplitude in the pairing frequency band of orbit resonance frequency of the impurity that exists in the concentration that is lower than the signal intensity that sets signal intensity with demonstration; And the quality analysis step of measuring the quality of above-mentioned detected object chemical substance or its fragment.
In the detection method of chemical substance of the present invention, the voltage amplitude that will be higher than the SWIFT waveform of the impurity institute respective frequencies that the concentration of setting signal intensity exists improves, and the voltage amplitude of the frequency of the part that impurity concentration is low reduces.Therefore, owing to can optionally remove the impurity of high concentration especially, remove the low impurity energy needed of concentration and can reduce.Therefore, the SWIFT energy needed seldom can be finished, in addition, owing to the supply unit miniaturization can be able to be need not to use excessive power supply, and comparatively economical., improve the impurity of SWIFT waveform voltage amplitude herein, the impurity of preferable object for existing with identical with the signal intensity of the detected object chemical substance at least concentration of signal intensity.In addition, be object though also can lack the impurity that mass number exists, yet if so, because the SWIFT energy needed becomes big, so preferable impurity with the signal intensities of signal intensity more than 5 one-tenth with above-mentioned detected object chemical substance is object.
In addition, the detection method of chemical substance of the present invention is characterized by and has: will contain the ion trap step of the ion swarm sealing of Ionized detected object chemical substance ion in section by electric field, magnetic field and other; To become big and SWIFT waveform that voltage amplitude dwindles offers above-mentioned ion swarm and removes step with the impurity of removing impurity along with contained frequency; And the quality analysis step of measuring the quality of above-mentioned detected object chemical substance or its fragment.
The detection method of chemical substance of the present invention, the impurity big for mass number provides and offers the energy of the energy same degree of the little impurity of mass number.Generally speaking, the orbit resonance frequency in the ion trap is the function of mass number, and mass number is big more, and then frequency is more little, and the frequency interval that is equivalent to mass number interval 1 becomes narrow and small.On the other hand, at document " Development of aCapillary High-performance Liquid Chromatography Tandem MassSpectrometry SyStem Using SWIFT Technology in an Ion Trap/ReflectronTime-of-flight Mass Spectrometer " in the past, Rapid Communication in MassSpectrometry, vol.11, in the generation of the SWIFT waveform that generally carries out among the 1739-1748 (1997) etc., be to carry out anti-Fourier (Fourier) conversion by the frequency spectrum that voltage amplitude is constant, and the conversion time field generates the SWIFT waveform.This kind situation with constant frequency interval, generates the waveform of the sinusoidal waveform sum with constant voltage amplitude.Thereby, this kind situation, because mass number is big more, the sinusoidal undulation number at average quality number interval 1 is few, average quality number 1 energy at interval also lacks.That is, the energy that is added on the big molecule of mass number relatively diminishes.
In contrast, because the voltage amplitude of the sine wave that the present invention will be less relatively increases revisal, also can provide sufficient energy to the big ion of mass number, thereby this kind impurity more positively can be removed.In addition, at the little ions of mass number,, can improve the service efficiency of energy owing to can in needed abundant scope, provide its energy.In addition, because of not needing excessive supply unit, but also reducing apparatus cost is set.
In addition, the detection method of chemical substance of the present invention is characterized by and has: the ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms; No matter the size of the mass number of the subject molecule of removing by SWIFT, the random waveform that produces the SWIFT waveform with the constant distribution of voltage amplitude produces step; And above-mentioned SWIFT waveform offered the ion swarm that is closed with after removing above-mentioned impurity in above-mentioned ion trap mechanism, measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
The detection method of this chemical substance will diminish and the frequency spectrum of the big SWIFT waveform of voltage amplitude amplitude variation along with frequency, when making mass number regard the transverse axis conversion, and the rough steady state value that becomes of voltage amplitude of average unit mass number.Therefore, to the molecule of any quality of the object removed by SWIFT, all can give rough constant energy.Thus, the ion big for mass number also can provide sufficient energy, this kind impurity more positively can be removed.In addition, at the little ions of mass number,, can improve the service efficiency of energy owing to can in needed abundant scope, provide its energy.In addition, because of not needing excessive supply unit, but also reducing apparatus cost is set.
In addition, the detection method of chemical substance of the present invention is characterized by and has: will contain ion trap step by the ion swarm sealing of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion by electric field, magnetic field and other mechanisms; With SWIFT waveform (it does not give voltage amplitude in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances) offer above-mentioned ion swarm to remove impurity the step of residual a plurality of detected object chemical substances; And the quality analysis step of the quality of the above-mentioned detected object chemical substance of mensuration or its fragment.
Because contained dioxin and precursor denier thereof in the exhaust of incinerator improves their detection precision, in that the instant situation about controlling of the burning condition of incinerator is very important.The detection method of chemical substance of the present invention, using does not provide the SWIFT waveform of voltage amplitude to remove impurity in corresponding to the frequency band of a plurality of detected object chemical substances.Then, a plurality of detected object chemical substances are detected simultaneously by quality analysis mechanism.Like this, because a plurality of detected object chemical substances are detected simultaneously, for example, even detect the degree of accuracy deficiency of each detected object material, to a plurality of materials in general, Yi Bian by asking for and the dioxin relevent information, Yi Bian estimate fired state, can carry out the high mensuration of degree of accuracy, also can improve the degree of accuracy of burning control.
In addition, the detection method of chemical substance of the present invention is characterized by and has: will contain ion trap step by the ion swarm sealing of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion by electric field, magnetic field and other mechanisms; SWIFT waveform (it does not provide voltage amplitude in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances) is offered above-mentioned ion swarm to remove the step of impurity and residual a plurality of detected object chemical substances; The little detected object chemical substance of mass number begins from above-mentioned a plurality of detected object chemical substances, gives the fragmentation step of fragmentation in regular turn: and the quality analysis step of the quality of the above-mentioned detected object chemical substance of mensuration or its fragment.
In the detection method of this chemical substance, the little detected object chemical substance of mass number begins from a plurality of detected object chemical substances that exist, and gives fragmentation in regular turn.Therefore, by the fragmentation of the little detected object chemical substance of mass number, can not destroy the material fragment bigger than this detected object chemical substance mass number.Thus, a plurality of detected object chemical substances all can be detected, thereby the sensitivity that can improve the quality and analyze, measure with pinpoint accuracy more.
In addition, the detection method of chemical substance of the present invention is characterized by and has: the ion trap step that will contain the ion swarm sealing of the different detected object chemical substance ion of Ionized a plurality of mass number by electric field, magnetic field and other mechanisms; SWIFT waveform (its in corresponding to a plurality of frequency bands of the mass number of a plurality of detected object chemical substances not service voltage amplitude) is offered above-mentioned ion swarm to remove the step of impurity and residual a plurality of detected object chemical substances; Provide the TICKLE waveform that contains corresponding at least 2 kinds of isotopic frequencies in the isotope of above-mentioned detected object chemical substance, with at least 2 kinds of fragmentation steps of carrying out fragmentation in the isotope of this detected object chemical substance; And the quality analysis step of the quality of the above-mentioned detected object chemical substance of mensuration or its fragment.
The detection method of this chemical substance provides in the isotope that comprises with above-mentioned detected object chemical substance the TICKLE waveform of the corresponding frequency of at least 2 kinds of isotopes, with in the isotope of this detected object chemical substance at least 2 kinds carry out fragmentation, for quality analysis.Like this, owing to use a plurality of isotopes in the quality analysis,, also can improve the detection degree of accuracy even have only the dioxin of denier or the situation that its precursor exists in the exhaust.In addition, in the situation of the burning control of use incinerator, also can improve the degree of accuracy of control.
In addition, being characterized as of the detection method of chemical substance of the present invention, in the above-mentioned quality analysis step in the detection method of above-mentioned chemical substance, with at least 2 kinds in the isotope of the fragment that generates by the detected object chemical substance as the instrumentation object.
The detection method of this chemical substance is with at least 2 kinds of objects as quality analysis in the isotope of the fragment that generated by the detected object chemical substance.Like this, owing to use the isotope of a plurality of fragments in the quality analysis,, also can improve the detection degree of accuracy even have only the dioxin of denier or the situation that its precursor exists in the exhaust.In addition, in the situation of the burning control of use incinerator, also can improve the degree of accuracy of control.
In addition, being characterized as of the detection method of chemical substance of the present invention, in the detection method of above-mentioned chemical substance, before above-mentioned ion trap step, have will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance.
In addition, being characterized as of the detection method of chemical substance of the present invention, above-mentioned ionization step, be will be higher than ionization potential and energy below the value that adds 4eV on this ionization potential offer above-mentioned detected object chemical substance.
The detection method of these chemical substances of the present invention, to can offer this detected object chemical substance by the little energy of sum than the ionization potential height of detected object chemical substance and than this ionization potential and above-mentioned detected object chemical substance ionic dissociation, with this detected object chemical substance ionization.Therefore, can not generate unnecessary fragment and since ionization do not destroy should be residual the detected object chemical substance under finish thereby the detection sensitivity that can improve the quality and analyze.Therefore, the action effect that produces with above-mentioned method of determining chemical complements each other, and the detection sensitivity of quality analysis mechanism is improved, and can measure by the pinpoint accuracy height.Then, in the burning control of incinerator, can control more densely.In addition,, need not to prepare excessive power supply, therefore can reduce the manufacturing cost of device owing to can reduce SWIFT voltage.
Description of drawings
Fig. 1 is the key diagram of pick-up unit of the chemical substance of expression embodiments of the present invention 1.
Fig. 2 is the process flow diagram of detection method of the chemical substance of expression embodiments of the present invention 1.
Fig. 3 (a) and Fig. 3 (b) are that expression is made as capture frequency when constant, with respect to the key diagram of the ion signal intensity distributions of RF voltage.
Fig. 4 (a) and Fig. 4 (b) are the key diagrams of the ion signal intensity distributions of relative RF frequency when representing the RF voltage constant.
Fig. 5 (a) and Fig. 5 (b) are the key diagrams of the relation of expression SWIFT frequency and relationship of amplitude and ion signal and mass number.
Fig. 6 is the key diagram of frequency spectrum of the SWIFT waveform of expression embodiments of the present invention 5.
Fig. 7 (a) and Fig. 7 (b) are the key diagrams of representing the frequency spectrum of SWIFT waveform in the past.
Fig. 8 (a) and Fig. 8 (b) are the key diagrams of the frequency spectrum of the relevant SWIFT waveform of expression embodiments of the present invention 6.
Fig. 9 is the key diagram of frequency spectrum of the SWIFT waveform of expression embodiments of the present invention 7.
Figure 10 (a) and Figure 10 (b) are the key diagrams of frequency spectrum of the TICKLE waveform of expression embodiments of the present invention 7.
Figure 11 (a)-Figure 11 (d) is the key diagram of representing the frequency spectrum of the TICKLE waveform of embodiments of the present invention 9, mass number being used as the transverse axis conversion.
Embodiment
Below, the limit explains with reference to accompanying drawing of the present invention limit.In addition, the present invention is not subjected to the qualification of this embodiment.In addition, in the inscape of following embodiment, even the personnel in present technique field are that expect easily or identical in fact being also included within the protection domain of the present invention.In the inscape of following embodiment, comprise the key element that those skilled in the art expect easily.
(embodiment 1)
Fig. 1 is the key diagram of pick-up unit of the chemical substance of expression embodiments of the present invention 1.The pick-up unit 100 of this chemical substance possesses: chamber 1, gas gatherer 2, as the vacuum ultraviolet light modulation 3 of ionization mechanism and as the flight time type mass analyzer 4 of quality analysis mechanism.Possess RF ion trap device 10 in the chamber 1, this RF ion trap device 10 possesses RF (the Radio Frequency: ring high frequency) as ion trap mechanism.Herein, the high-frequency electric field by forming in inside is closed in the detected object chemical substance in the Ionized exhaust in the grabber 11.
Can use by electric field, magnetic field or other electromagnetic strength ion is closed in inner mechanism.In addition, can distinguish and use electric field or magnetic field etc. individually, also they can be made up aptly and use.This kind ion trap mechanism is known several, wherein forms the above-mentioned RF ion trap device 11 of high-frequency electric field in inside, because operation is more preferable than being easier to event.In addition, other ion trap mechanisms except that this kind RF type, also can use penning formula (Penning) grabber that produces by DC voltage and static magnetic field.
As the RF ion trap device 10 of ion trap mechanism, constituted by the first terminal sealing cap (endcap), 12, second terminal sealing cap 13 and RF ring king 4, be three-dimensional four polar forms.As shown in Figure 1, RF ring 14 is the inside that is configured in the first terminal sealing cap 12 and the second terminal sealing cap 13.In addition, on RF ring 14, connect and be used to add the high intensity light source 21 of catching voltage, HF voltage is added on RF ring 14 outward with as catching voltage.By this high frequency the detected object chemical substance in the Ionized exhaust and other materials are closed in the grabber 11.In addition, first and second terminal sealing cap 12 and 13 is connected in the random waveform generation device 20 that produces mechanism as random waveform, when following SWIFT and TICKLE, adds the voltage with characteristic frequency between two terminal sealing caps.
Possess gas injection tube 5 in the gas gatherer 2, playpipe 5 is formed by the switch valve or the kapillary of use as the spray orifice (orifice) of pulse valve.The exhaust Gs that is imported into the incinerator etc. of gas injection tube 5 is imported into chamber 1.Well heater 6 is set around the gas injection tube 5.Well heater 6 is to be used to prevent that the detected object chemical substance is attached to the heating arrangement of the inwall of gas injection tube 5.
Chamber 1 possesses the vacuum ultraviolet light modulation 3 as ionization mechanism, makes its ionization so that energy to be provided to the detected object chemical substance.Vacuum ultraviolet light modulation 3 is by rare gas such as Ar, Kr or Xe, or with H 2, O 2Or Cl 2Deng the discharge that makes an addition to the gas among Ar, the He, produce vacuum-ultraviolet light L.In the present embodiment, use the Lyman α light that comes from hydrogen plasma with 121.6nm wavelength.
Vacuum ultraviolet light modulation 3 can change the photon energy of the vacuum-ultraviolet light that is produced by the kind of conversion discharge gas.Therefore, cooperate the ionization potential of detected object chemical substance, can provide bigger but do not make the photon energy of the degree that the detected object chemical substance dissociates than this.Thus, can stop the ionization that is mingled with material, suppress the fragmentation of detected object chemical substance simultaneously with ionization potential higher than photon energy.
In addition, ionization mechanism also can use laser instrument or other high frequency waves to replace vacuum ultraviolet light modulation 3.This kind situation by using wavelength variable laser instrument, changes the photon energy of generation, can screen ionised species.Wavelength variable laser can be used well-known laser instrument.In addition, applicable vacuum-ultraviolet light among the present invention with the following wavelength of the above 200nm of 50nm, and being preferable below the above 200nm of 100nm, suppress viewpoint for still less from generation with unwanted fragment, with more than the 112nm to the scope of 138nm for better.
In addition, as providing energy to make its Ionized mechanism, can use laser instrument or quasi-molecule light modulation (eximer lamp) with ultraviolet wavelength to the detected object chemical substance.In addition, also can in particle accelerator, hit for example He ion plasma, impact contained detected object chemical substance in the sample gas in the chamber 1.In addition, also available fan-shaped device (sector) separates electron beam, takes out the ion with 10eV left and right sides energy, impacts contained detected object chemical substance in the sample gas in the chamber 1.
As the flight time type mass analyzer 4 of quality analysis mechanism, the ion for the detected object chemical substance in the ionization exhaust in the chamber 1 identifies the detected object chemical substance by measuring its quality.Ionizable detected object chemical substance on the second terminal sealing cap 13 that will add to RF ion trap device 10 with the extraction voltage of pulse type, and is imported in the mass analyzer 4 and flight in mass analyzer 4 outward.The ion of flight detects by ion detector 30, and after detected herein signal increased by prime amplifier 31, input data processing equipment 32 carried out data processing.In addition, in the present embodiment, in ion detector, use microchannel plate (microchannelplate), can improve the detection sensitivity of ion.Mass analyzer 4 is measured its flight time.Owing to the corresponding relation of height is arranged, between the quality of flight time and flight material by the quality of flight time detection flight material, from this Quality Identification material.
Then, use Fig. 2 that the pick-up unit 100 that uses chemical substance is described, detect order as the precursor of detected object in the exhaust.Herein, Fig. 2 is the process flow diagram of detection method of the chemical substance of expression embodiments of the present invention 1.At first, the exhaust Gs with incinerator imports in the chamber 1 (step S101).Then, import the exhaust Gs irradiation vacuum-ultraviolet light L of chamber 3 by 3 pairs of vacuum ultraviolet light modulations, exhaust Gs accepts from vacuum-ultraviolet light L and the photon energy of coming and be ionized (step S102).Wherein, as the ionization potential of the precursor of detected object material in the scope of 8.5～10.0eV.In addition, as above-mentioned mode, employed vacuum-ultraviolet light in the present embodiment has the wavelength of 121.6nm, and its photon energy is 10.1eV.Like this, because the energy bigger slightly than the precursor ion current potential only is provided, therefore can under the situation that unnecessary energy is not offered precursor, make precursor ionization.
As a result, efficiently instrumentation as the precursor of Ionized detected object chemical substance.This is that Ionized precursor almost all can be used as the determination object of mass analyzer 4 because in the ionization that vacuum-ultraviolet light produces, the generation of fragment is considerably less.Especially, owing to from the next exhaust of incinerator, only exist the precursor of denier, so its effect is very big.In addition, the capture rate that can suppress grabber 11 reduces.Wherein, the ion of fragmentation by being closed in the ionic potential that ion generated in the grabber 11, has the effect of the current potential of offsetting grabber for a long time.Yet because the ionization that this kind vacuum-ultraviolet light produces can suppress the generation of unnecessary fragmention to minimum, the capture rate that therefore can suppress ion trap device 11 reduces.
In addition, the SWIFT voltage of following explanation can be reduced.Herein, so-called SWIFT is meant in order to remove impurity, provides between the first terminal sealing cap 12 of grabber 11 and the second terminal sealing cap 13 and the operation of conversion ion trajectory by the voltage waveform that will have characteristic frequency.Produce in many ioning methods at fragment, produce as the precursor of detected object chemical substance or with a large amount of fragments of other materials in the mass number that in the SWIFT process, should remove as affinity molecule.For it is removed with SWIFT, need very large voltage, therefore need the big SWIFT device for generating voltage (Arbitrary Waveform Generator) of output.On the other hand, if SWIFT voltage is increased, the molecule of the mass number beyond the mass number that destroy also will go to pot, thereby want residual precursor also to go to pot.As a result, cause the reduction of analytical precision in the quality analysis.
Because the generation of fragment is considerably less in the ionization of the present invention, it is few that the fragment that should remove in the process of SWIFT also becomes.As a result owing to reduce SWIFT voltage, can do not destroy should be residual precursor under finish the removal of impurity, therefore almost can avoid above-mentioned problem points fully.In addition, for affinity molecule residual behind the SWIFT or pay when TICKLE described later or the cooling, in the many ioning methods of fragment, also produce fragments from various affinity molecules.As a result, as the fragment beyond the purpose precursor contained into and become impurity, and cause the reduction of analytical precision in the quality analysis.Yet if according to method of the present invention, the fragment that produces during owing to ionization is few, and this problem also almost can be avoided.
Be illustrated at SWIFT then.This is to be used for removing the detected object chemical substance not operation of material in addition that exhaust exists.Therefore, in the first terminal sealing cap 12 of RF ion trap device 10 and and the second terminal sealing cap 13 between, add the voltage of the broadband frequency corresponding with the orbit resonance frequency of the material that will remove by random waveform generation device 20.Thus, form the mechanism that impurity of the present invention is removed.In addition, get rid of the orbit resonance frequency corresponding from this broadband frequency with the frequency of detected object chemical substance mass number.Thus, the material that remove becomes with large-amplitude vibration, impacts the wall of RF ion trap device 10, loses electric charge, no longer exists with ion.And the detected object chemical substance is encircled 14 the voltage of catching by being added on RF outward, and former state is closed in the grabber 11.This kind operation is called SWIFT, can remove detected object chemical substance impurity (step S103) in addition by this operation.
Be illustrated at TICKLE then.TICKLE makes detected object chemical substance fragmentation, the operation that will separate with the detected object chemical substance with the impurity that detected object chemical substance mass number is similar to.Then, measure the mass number of the fragment that generates from molecule, to identify the detected object chemical substance as the detected object chemical substance of affinity molecule.In addition, if measure the amount of this fragment, also can try to achieve the concentration of detected object chemical substance.TICKLE is different with above-mentioned SWIFT, with corresponding to frequency as the orbit resonance frequency of the detected object chemical substance of affinity molecule, with voltage be added on outward the first terminal sealing cap 12 and and the second terminal sealing cap 13 between.At this moment, by random waveform generation device 20, the voltage of said frequencies is added on outward between the above-mentioned end sealing cap.Thus, constitute fragmentation of the present invention mechanism.Then, the ion that makes the detected object chemical substance conflicts with other materials in coexisting as grabber 11, with detected object chemical substance fragmentation.Thus, promptly finish (step S104) based on the fragmentation of TICKLE.
After finishing based on the fragmentation of TICKLE, stop to encircle 14 impressed voltages, by will adding to the second terminal sealing cap 13 outward, the ion of the detected object chemical substance of fragmentation is led to mass analyzer 4 (step S105) side with the voltage that pulse type is drawn for RF.Allow the ion of this detected object chemical substance in mass analyzer 4, fly.Measure its flight time by mass analyzer 4.As above-mentioned mode,,,, finish mensuration (step S107) at last by this Quality Identification material (step S106) by the quality of flight time detection flight material because the corresponding relation of height is arranged between the quality of flight time and flight material.
The flight time type mass analyzer that uses in the present embodiment because several 10 μ finish instrumentation once second, has the advantage of what is called " the instrumentation time is very fast, and irritability is good ".Therefore, especially suitable during with immediate mode control burning condition in the factory of reality.In addition, about other quality analysis mechanisms, also can use quality analysis mechanisms such as electric field type or RF coil form.Especially RF coil form, owing to can be only in the outlet of grabber 11 ion detector be set, available simple structure constitutes mass analyzer.
(embodiment 2)
The pick-up unit 100 of chemical substance of the present invention is with the exhaust vacuum-ultraviolet light direct irradiation that imports in the grabber 11, with the ionization of instrumentation object material.Then, impose SWIFT and TICKLE in herein, with the fragment ionization of instrumentation object material.Therefore, with this case before the same condition of ionization under, SWIFT or fragmentation sometimes may not be successful.Therefore, be illustrated at the condition of SWIFT and TICKLE herein.Fig. 3 be expression with the grabber frequency when constant with respect to the key diagram of the ion signal intensity distributions of RF voltage.In addition, Fig. 4 is expression key diagram with respect to the ion signal intensity distributions of RF frequency during with the RF voltage constant.
With the ionization of the combination results beyond the employed vacuum-ultraviolet light before this case, be that outside at grabber 11 is with the ionization of detected object chemical substance.And, during with detected object chemical substance fragmentation, be to be supplied in grabber 11 inside with gas, with detected object chemical substance fragmentation from the outside with impacts such as inert gas or nitrogen.Therefore, Atmospheric components such as contained water vapor or oxygen are present in grabber 11 inside hardly in the exhaust as determined gas.Therefore, show as Fig. 3 (a) figure or the represented ion signal intensity distributions of Fig. 4 (a).
Yet ioning method of the present invention is that the vacuum-ultraviolet light direct irradiation is imported into exhaust in the grabber 11, with the ionization of detected object chemical substance.Therefore, exist Atmospheric components such as existing water vapor or oxygen in the exhaust in the grabber 11.Under the environment of Atmospheric components such as this kind water vapor or oxygen and the coexistence of detected object chemical substance, if add following TICKLE voltage with detected object chemical substance fragmentation, producing fragment sometimes can't captive situation.For example, if RF voltage surpasses 1500V, fragment can't be hunted down (Fig. 3 (b)).In addition, if the RF frequency is less than 1.0MHz, fragment also can't be hunted down (Fig. 4 (b)).Herein, contact conditions is meant the outer RF voltage of RF ring 14 and the value of RF frequency of being added on.Consider reason wherein, because above-mentioned water vapor (also being hydrone) or oxygen molecule have polarity, it is big that the ion trajectory of the detected object chemical substance of fragmentation becomes, and the wall of this bombardment by ions grabber 11 loses the event of electric charge as a result.
Therefore, even, be necessary to adjust contact conditions in order under hydrone or oxygen molecule coexistence, also to be hunted down by the ion of the detected object chemical substance of fragmentation.For example, with TCB (mass number 180,182,184) during as affinity molecule, measure from its take out a chlorine fragment (mass number 145,147), take out fragment (mass number 109,111) of two chlorine and a hydrogen and take out the fragment (mass number 74) of three chlorine and a hydrogen from it from it.In method in the past, when being 1.0MHz, RF voltage is adjusted to below the above 2000V of 1000V as if the RF frequency, can suitably catch fragmention (with reference to figure 3 (a)).
Under the coexistence of oxygen and hydrone, in the same frequency condition, if RF voltage is adjusted to below the above 1300V of 700V, can catch well, in addition, if RF voltage is adjusted to below the above 1100V of 900V, can more stably catch fragmention (with reference to figure 3 (b)).In addition, RF voltage is adjusted under the situation of 1600V, and the RF frequency is suitably with 1.0MHz in the previous methods, yet in this method, as if the scope that the RF frequency is adjusted to below the above 1.7MHz of 1.2MHz, can stably fragmention be caught.In addition, as if the scope that the RF frequency is adjusted to below the above 1.6MHz of 1.4MHz, can more stably fragmention be caught (with reference to figure 4 (b)).
(embodiment 3)
During SWIFT, be necessary to improve as having the capture rate of the instrumentation object material of high-quality affinity molecule.On the other hand, during TICKLE, be necessary to improve capture rate as the instrumentation object material of fragmentation with inferior quality number.Therefore, during SWIFT, the energy value (also being the long-pending of RF voltage and RF frequency) that is added on RF ring 14 is outward improved.And, during TICKLE, RF voltage and the long-pending of RF frequency are diminished.By this kind mode, in the time of can improving SWIFT and TICKLE, the capture rate of instrumentation object material or its fragment.
For example, with the RF frequency constant be 1MHz, catch with 1600V during SWIFT, catch with 1000V during TICKLE.In addition, can be 1600V also with the RF voltage constant, catch with RF frequency 1.4MHz during SWIFT, catch with 1.0MHz during TICKLE.In addition, also can aspect RF frequency and RF voltage two, change.In addition, this variation can be that step response changes, and also can carry out with the mode that gradually changes.In addition and since the detected object chemical substance with certain certain life-span from grabber 11 to outside loss, therefore can suitably change towards the direction that shortens the TICKLE required time.Particularly, can improve the voltage of TICKLE.
The detected object chemical substance is by behind the TICKLE fragmentation because mass number also becomes than little before the fragmentation, therefore after being less than TICKIE and ending must outside be added on RF ring 14 RF voltage become than little before the TICKLE, or the RF frequency is become greatly.Yet, if make the outer RF voltage that is added on RF ring 14, or the RF frequency is changed towards becoming big direction towards the direction that diminishes, the capture rate of the fragment that mass number is little will reduce.Therefore, under this kind state, if after TICKLE is ended through time too for a long time, this fragment will reduce and the detection sensitivity of mass analyzer 4 will reduce.Therefore, behind the input TICKLE waveform, behind detected object chemical substance fragmentation effluxion, it is preferable to carry out switching to of aforesaid way immediately.
(embodiment 4)
Among the SWIFT, though remove material beyond the detected object chemical substance, must remove this moment is the impurity with mass number of the fragmentation ion same degree that produces with detected object chemical substance fragmentation the time.Because in based on the quality analysis behind the fragmentation of TICKLE, with determined, the instrumentation degree of accuracy of detected object chemical substance will reduce this impurity as a result with fragmention.In addition, if the impurity beyond above-mentioned when being present in the grabber 11 in a large number, will make grabber 11 saturated, and capture rate reduces, and therefore preferably the material beyond the detected object chemical substance be removed when the SWIFT as possible.
Yet,, must add the SWIFT waveform that has corresponding to the frequency content of very broad mass number scope for the impurity beyond the detected object chemical substance is removed fully.Yet, the SWIFT waveform with frequency content of broad range, because the average energy of cell frequency is little, the energy that can be added on the molecule with certain mass number also diminishes.As a result, the efficient of removing of impurity reduces, and the detection degree of accuracy of detected object chemical substance also reduces.Therefore, when being added on the SWIFT waveform of the frequency content with broad range, the output that must maybe will amplify the amplifier of its output on the one hand as high frequency generation device 21 high performances in SWIFT waveform generation source increases, so that the expanded range of amplification frequency.As a result, the device maximization that will become, price uprises simultaneously.
Therefore, the mass spectrum of impurities in the investigation exhaust, the SWIFT waveform of the frequency content by having the mass number scope that must remove corresponding to bottom line is removed impurity.The mass number scope that bottom line must be removed for example, can be that the impurity of the value more than the certain value is determined by containing the signal intensity with mass spectrum.Preferably with have this certain value at least for the signal intensity same degree of instrumentation object chemical substance maybe the impurity of the signal intensity more than this value be object.In addition, though also the impurity that can exist with mass number still less is object, yet if so, it is big that the SWIFT energy needed becomes.Therefore, the impurity with the signal intensity of 5 one-tenth above intensity of signal intensity with instrumentation object chemical substance is that object is preferable.
In the example of certain incinerator and since for example mass number 48 or more the scope below 355 be the bottom line scope that must remove, remove impurity by having corresponding to the SWIFT waveform of this range frequencies composition.If so, the energy that then drops into grabber 11 is unlikely to excessive, also the detected object chemical substance can be measured with degree of accuracy enough in the practicality.Thus, there is no need to use excessive device, the cost of device can be forced down.
(embodiment 5)
Fig. 5 is the key diagram of the relation of expression SWIFT frequency and relationship of amplitude and ion signal and mass number.Herein, the mass number among Fig. 5 is corresponding to the SWIFT frequency among the figure.In addition, Fig. 6 is the key diagram of frequency spectrum of the SWIFT waveform of expression embodiments of the present invention 5.Frequency spectrum is with the intensity (voltage amplitude) of SWIFT waveform or the TICKLE waveform function representation corresponding to the frequency of SWIFT waveform etc.In order to remove the very high impurity of concentration, though must add very high SWIFT voltage, among the SWIFT in the past, be that the frequency that will be equivalent to all mass numbers adds with identical voltage amplitude.That is, SWIFT voltage is determined by removing the needed voltage of the highest impurity of concentration.Therefore, when removing the very high impurity of concentration, all be necessary for very high amplitude owing to become, the service efficiency of energy reduces.
In addition, because that supply unit also is necessary for is capacious, cause cost to increase.In addition, for keeping as the affinity molecule of detected object chemical substance, though will from the SWIFT waveform, get rid of corresponding to the frequency band of the mass number of this detected object chemical substance, yet under the situation of applying high voltage amplitude, even only get rid of same frequency band, in fact residual mass number scope is diminished.As a result, some detected object chemical substance also is removed, and the problem of what is called " detecting degree of accuracy reduces " is arranged.It is former because frequency spectrum of actual SWIFT waveform is not the represented ideal rectangle of solid line as Fig. 5 (a), and become the shape of the represented rough fan out of the dotted line of Fig. 5 (b) so.That is, because the frequency spectrum of SWIFT waveform is actually the shape of rough fan out, the represented frequency band corresponding to the mass number of detected object chemical substance of Δ F diminishes among the figure, so that detects degree of accuracy and reduce.
Therefore, as shown in Figure 6, will improve corresponding to the voltage amplitude of the SWIFT waveform of the frequency of the mass number of high concentration impurities, and, then reduce voltage amplitude for the low part of the concentration of impurity.Like this, the extra high impurity of concentration optionally can be removed.Herein, the impurity that the voltage amplitude of SWIFT waveform is improved is object with the impurity that has at least with the signal intensity of the signal intensity same degree of instrumentation object chemical substance preferably.In addition, though also the impurity that can exist with few mass number is object, yet if so, it is big that the SWIFT energy needed becomes.Therefore, be object preferably with the impurity of the signal intensity of 5 one-tenth above intensity of signal intensity with instrumentation object chemical substance.By this mode,, therefore can improve the energy service efficiency and remove impurity owing to generally speaking can force down the voltage amplitude of SWIFT waveform.In addition, because supply unit also can use the little device of capacity, therefore the supply unit miniaturization also can be forced down cost.In addition, even carry out the SWIFT operation, owing to can positively the detected object chemical substance be kept the detection degree of accuracy of the analysis meter 4 that therefore also can improve the quality.
(embodiment 6)
Fig. 7 is a key diagram of representing the frequency spectrum of SWIFT waveform in the past.Fig. 8 is the key diagram of frequency spectrum of the SWIFT waveform of expression embodiments of the present invention 6.Herein, (b) among two figure is the frequency spectrum with the SWIFT waveform, as transverse axis, promptly is transformed to the function of mass number with mass number.Common SWIFT waveform, even for the resonant frequency with ion becomes big, the also constant rectangle frequency spectrum of the size of amplitude is carried out anti-Fourier (Fourier) conversion and is produced (Fig. 7 (a)).The SWIFT waveform of this moment becomes the overlapping waveform of resonant frequency corresponding to the impurity mass number that will remove.This waveform comprises all the orbit resonance frequencies corresponding to mass range ideally, is successional waveform.Yet in fact owing to must carry out anti-Fourier transform based on the data of limited resonant frequency, the contained frequency content of resulting SWIFT waveform becomes discrete, and its frequency difference becomes constant.If on the contrary it is scaled mass number, the regional medium frequency spacing that mass number is big becomes slightly wide, and the regional medium frequency spacing that mass number is little becomes carefully narrow.
If use this kind SWIFT waveform, the ion that mass number is little can be given amplitude by high-energy-density, and on the contrary, the ion that mass number is big can only be given amplitude (Fig. 7 (b)) with little energy density.Therefore, the ion that mass number is little can easily destroy, and the big ion of mass number is difficult to destroy, the residual impurity that becomes.And, because TICKLE produces unnecessary fragment, make the degree of accuracy of quality analysis reduce.
Therefore, use will frequency spectrum that voltage amplitude diminishes be carried out the SWIFT waveform that anti-Fourier transform generated (Fig. 8 (a)) along with becoming big corresponding to the resonant frequency of mass number.If plant mode according to this, can provide sufficient energy (Fig. 8 (b)) for the big ion of mass number.That is, no matter, therefore, can more positively remove the big ion of mass number because the mass number size of the subject molecule of removing based on SWIFT all provides the SWIFT waveform with the constant distribution of voltage amplitude (Fig. 8 (b)).
In addition, at the little ions of mass number,, can improve the service efficiency of energy owing to can in the abundant scope of needs, provide its energy.In addition, because of not needing excessive supply unit, also can lower cost is set.
(embodiment 7)
Fig. 9 is the key diagram of frequency spectrum of the SWIFT waveform of expression embodiments of the present invention 7.In addition, Figure 10 is the key diagram of frequency spectrum of the TICKLE waveform of expression embodiments of the present invention 7.The pick-up unit 100 of this chemical substance, during as the detected object chemical substances such as precursor of dioxin, a plurality of detected object chemical substances of instrumentation can further improve the detection degree of accuracy simultaneously at instrumentation.Especially, because contained dioxin and precursor denier thereof in the exhaust of incinerator improves their detection degree of accuracy, very important in the situation of the burning condition of control incinerator when in sight.
Therefore, because with a plurality of detected object chemical substances while instrumentations, when SWIFT, use will be adjusted to corresponding to the voltage amplitude in the resonant frequency band of the mass number of this detected object chemical substance 0, promptly do not give the SWIFT waveform frequency spectrum (Fig. 9) of voltage amplitude.In addition, the frequency spectrum of this SWIFT waveform is carried out anti-Fourier transform, generate the SWIFT waveform.If use the SWIFT waveform after this inverse transform to apply SWIFT, then this detected object chemical substance still is closed in the grabber 11 of ion trap device 10, therefore can separate with other impurity.
Secondly, carry out anti-Fourier transform, generate the TICKLE waveform, detected object chemical substance fragmentation (Figure 10 (a)) by the TICKLE frequency spectrum that has large amplitude in will frequency band corresponding to above-mentioned detected object chemical substance mass number.In addition, with the ion of the detected object chemical substance of fragmentation with mass analyzer 4 (with reference to Fig. 1) instrumentation, identification and detection object chemical substance, and ask for its concentration.In addition, also can carry out anti-Fourier transform, generate the TICKLE waveform, apply TICKLE (Figure 10 (b)) by containing the TICKLE frequency spectrum that has large amplitude in the scope corresponding to all frequencies of above-mentioned a plurality of detected object chemical substance mass numbers.In addition, also each frequency corresponding to the mass number of above-mentioned a plurality of detected object chemical substances can be applied in regular turn one by one.
(embodiment 8)
As mentioned above, if, can improve the detection degree of accuracy, thereby be preferred with a plurality of detected object chemical substances instrumentation side by side.Yet, simultaneously during a plurality of detected object chemical substance of instrumentation, have problem described as follows.For example, TCB (trichloro-benzenes) and DCB (dichloro-benzenes) are once obtained in the situation of fragment figure as affinity molecule, the fragment of TCB, mass number is 145, with mass number be that the mass number of 146 DCB only differs 1.Therefore, if TCB and DCB are imposed TICKLE simultaneously, because the TICKLE frequency of DCB, and make approaching TCB fragment some that ruined situation be arranged.Like this, by with the TCB fragmentation, so that TCB when separating with the impurity of TCB same degree with mass number, becomes and can't try to achieve the concentration of TCB etc. by measuring the signal of this fragment.As a result, the detection degree of accuracy of TCB reduces.Therefore, in the TICKLE of embodiment 7, note or correctly give corresponding to the frequency of mass number or with the suitable propertyization of TICKLE voltage.And, noted that even so the suitably situation of fragmentation is also arranged.
Therefore, in the mode of the present invention, destroy with TICKLE, carry out fragmentation, detected object chemical substance in the mass number scope of this detected object chemical substance or impurity etc. are removed from the detected object chemical substance that mass number is little.In addition, the detected object chemical substance bigger to mass number imposes TICKLE, in the mass number scope that the little detected object chemical substance of above-mentioned mass number exists, the fragment of the big detected object chemical substance of this mass number produced.
If plant mode according to this, when the detected object chemical substance that mass number is big is carried out fragmentation, because the little detected object chemical substance of mass number is fragmentation, the fragment of the detected object chemical substance that above-mentioned mass number is big can not destroyed by the TICKLE of the little detected object chemical substance of mass number.Therefore, even a plurality of detected object chemical substances that mass number is different detect simultaneously, also can carry out the high mensuration of degree of accuracy.
Particularly, consider the situation that TCB (mass number 180,182,184,186), DCB (mass number 146,148,150) and MCB (monochloro benzene, mass number 112,114) detect simultaneously.Before TICKLE, other impurity is removed in these detected object chemical substances reservations by SWIFT.Then,, will be added on first and second terminal sealing cap 12 and 13 outward, generate the fragment of mass number 77 corresponding to the TICKLE frequency of MCB mass number for the MCB fragmentation.At this moment, in the grabber 11 of ion trap device 10, there is not the material of mass number 112-114.
Behind the MCB fragmentation, add TICKLE frequency corresponding to the mass number of above-mentioned DCB with the DCB fragmentation.This fragment is the mass number 111 and 113 of separating a chlorine from DCB, reaches the mass number 75 that two chlorine are separated with a hydrogen.At last, add frequency corresponding to the mass number of above-mentioned TCB with the TCB fragmentation.The mass number 145,147 and 149 of the fragment that generated this moment for a chlorine is separated, and the mass number 109 and 111 that two chlorine are separated with a hydrogen, and the mass number 74 that three chlorine are separated with a hydrogen.In addition, above-mentioned fragment is set the mistiming to a certain degree respectively, adds each TICKLE frequency one by one.
If the fragmentation of detected object chemical substance finishes, between first and second the terminal sealing cap 12 and 13 that voltage is not added to ion trap device 10 outward, and the fragmention in the grabber 11 is cooled off (cooling).Cool off the neutral gas that is meant in fragmention and the grabber 11 and impact and degradedness, fragmention can be cooled off thus.By cooling, the degree of accuracy of the quality instrumentation that mass analyzer 4 carried out is improved.
Cooling adds to outward in the second terminal sealing cap 13 by the voltage of will draw after finishing, and above-mentioned fragment is guided in the mass analyzer 4, by measuring its quality, can measure the concentration of detected object chemical substance.Particularly, the concentration of MCB can be selected the fragment signal intensity of mass number 77 and try to achieve, and the concentration of DCB can be selected the fragment signal intensity of mass number 113 and 75 and try to achieve.And the concentration of TCB can be selected the signal intensity of mass number 145,147,149,109 and 74 etc., tries to achieve with the nonoverlapping mass number of the fragment of above-mentioned MCB and DCB.
In addition, between the nonoverlapping detected object chemical substance of mass number (for example TCB and TCP) of the fragment that generates from the detected object chemical substance, can destroy by the TICKLE waveform simultaneously each other.For example,, then DCB and DCP are destroyed, at last TCB and TCP are destroyed, simultaneously six kinds of detected object chemical substances of instrumentation at first with MCB and MCP fragmentation.In addition, in this situation, because with two kinds of fragmentations respectively, the needed time of fragmentation is for independent when a kind of about 3 times are just finished.
(embodiment 9)
Sometimes has isotope in the detected object chemical substance, even also can have the different quality number as same detection object chemical substance.For example, MCB has the isotope of mass number 112 and 114.This be since the mass number of the chlorine of phenyl ring combination have 35 and 37 two kind so.Have in the isotopic detected object chemical substance of this kind, because a kind of density of detected object chemical substance of mass number, the density more all than this detected object chemical substance is low, if only with the instrumentation object material of a kind of mass number as mass analyzer 4, then cause the reduction of instrumentation sensitivity.
If is example with above-mentioned MCB, only with the MCB of mass number 112 during as the instrumentation object, MCB that can't instrumentation mass number 114.As a result, can't from MCB is all, be told, make detected concentration reduce by the MCB of the mass number 114 of instrumentation.Especially, the precursor as the dioxin of detected object chemical substance in the exhaust of incinerator because its concentration is extremely low, also is necessary even improve a little detection sensitivity.
Therefore, if incite somebody to action the wherein whole fragmentations of isotope of at least 2 detected object chemical substances, can avoid the problem of above-mentioned what is called " instrumentation sensitivity reduction ".Herein, the isotope of enumerating TCB is that example is illustrated, yet applicable object of the present invention is not limited to TCB, so long as it is all applicable to have isotopic detected object chemical substance.Figure 11 is the frequency spectrum of the TICKLE waveform of expression embodiments of the present invention 9, mass number is used as the key diagram of transverse axis conversion.In addition, represent the isotopic distribution of TCB ion with figure (a).
For example, can or with the whole isotope fragmentations of detected object chemical substance, or remove from the isotopes that whole isotopes will concentration be low in theory, perhaps impurity is sneaked into the isotope fragmentation of the detected object chemical substance that the many mass numbers of ratio remove.The TICKLE waveform of this moment can use the frequency spectrum of will be in comprising corresponding at least 2 detected object chemical substances giving large amplitude in the broad resonant frequency band scope of whole isotopic mass numbers, carries out anti-Fourier transform and obtains (Figure 11 (b)).
In addition, because resonant frequency has certain amplitude for the influential mass number of ion, when using the frequency spectrum of amplitude constant, the what is called phenomenon of " maximum with the minimum isotope of mass number is difficult to pay in TICKLE, and middle isotope is relatively paid in TICKLE easily " is arranged.Therefore, if formation all can be paid the frequency spectrum of the voltage amplitude amplification of isotopic mass number largest portion of detected object chemical substance and least part in slightly constant TICKLE for a plurality of isotopes as the TICKIE object.By this mode, can make its fragmentation slightly equably.In addition, also can form and to amplify the frequency spectrum that the voltage amplitude of the moderate part of mass number relatively dwindles (solid line of Figure 11 (c)) as the voltage amplitude of mass number largest portion and least part in the isotope of fragmentation object.In addition, also can use in the low isotope of the signal intensity relativity of ion the frequency spectrum that the isotopic voltage amplitude that voltage amplitude is higher relatively than ion signal intensity is little (dotted line of Figure 11 (c)).
On the other hand, also have and a large amount of situations about existing of the impurity of the rough identical mass number of a certain isotope.For example, Figure 11 (d) is for having and a large amount of situations about existing of the impurity of the TCB isotope equal in quality number of mass number 180.In this kind situation, will remove this isotopic a plurality of isotope fragmentations, not make under a large amount of impurity fragmentations, carry out the high instrumentation of degree of accuracy.In this kind situation, can use also that selection does not contain a plurality of isotopes that too many equal in quality is counted impurity from this isotope (herein as TCB isotope), the frequency spectrum that will form from a plurality of resonant frequencies corresponding to its mass number is carried out the TICKLE waveform (Figure 11 (d)) of anti-Fourier transform.
(embodiment 10)
Sometimes also exist isotope in the detected object chemical substance, and similarly also exist isotope in the fragment of detected object chemical substance.Therefore, about the mensuration of fragment, also exist and embodiment 8 described same problems.In the past, be the concentration of only measuring the detected object chemical substance with a fragment, the perhaps figure comparison that occurs by fragment, the concentration of estimation detected object chemical substance.
Yet, as the precursor of dioxin contained in the exhaust of incinerator, in the material that has only extremely low concentration to exist, only measure the isotope of a fragment, can't obtain the mensuration of abundant sensitivity.In addition, even the pattern comparison that produces based on a plurality of fragments, only absolute amount of debris is few in an isotope, with statistical estimated concentration and correct inadequately.
Thereby, with the isotope of the fragment that generates from the detected object chemical substance at least 2 kinds as the instrumentation object.Particularly, in the spectrum (signal voltage) of certain fragment, the value that the maximal value of the isotope spectrum of a plurality of appearance is added respectively, perhaps, the value that the area of the isotope spectrum of a plurality of appearance is added is respectively used as the calculated value of quality analysis 4.If this kind mode, owing to the isotope of certain fragment all can be used, even the extremely low situation of concentration of instrumentation object material in the mensuration of mass analyzer 4, also can improve instrumentation sensitivity.In addition, the situation of impurity fragment etc. in certain isotopic mass number, occurs, and when having the big spectrum of noise composition, select to remove the isotopic mass number of this isotope spectrum, can try to achieve the concentration of instrumentation object material.According to this mode, but because the noise of despumation etc. can obtain the higher instrumentation of degree of accuracy.
As mentioned above, the checkout gear of chemical substance of the present invention is with the detected object chemicals During the matter ionization, will be than the ionization potential of detected object chemical substance big and than this ionization potential Offer this detected object chemistry with the energy with little of above-mentioned detected object chemical substance ionic dissociation energy Material. Therefore, because destructive test object chemical substance and can ionization not in addition, is passed through SWIFT The generation of unnecessary fragment that becomes problem when removing impurity is few. Therefore, can be in that do not destroy should be residual Finish the removal of impurity under the detected object chemical substance, and the detection sensitivity that improves quality analysis mechanism Degree. In addition, owing to only give the SWIFT waveform, can remove neatly impurity when removing impurity. Cause This owing to can improve the detection speed of detected object chemical substance, is suitable for the control of actual incinerator System.
In addition, in the checkout gear of chemical substance of the present invention, by the TICKLE waveform is provided Fragmentation mechanism is detected object chemical substance fragmentation, even corresponding to the detected object chemical substance The frequency band of quality number in impurity is arranged, also can get rid of its impact, correctly measure. In addition, because from The fragment that takes place during sonization is few, with the situation of detected object chemical substance fragmentation, and can be with object The detected object chemical substance efficient ground fragmentation is arranged. As a result, can improve the detection of quality analysis mechanism Sensitivity, the control of can more critically burning.
In addition, in the checkout gear of chemical substance of the present invention, in ionization mechanism, provide energy Amount is during to the detected object chemical substance, described energy Ratios ionization potential height, and in this ionization potential On add below the value of 4eV. In addition, the energy by light is during with the ionization of detected object chemical substance, Its wavelength is below the above 200nm of 50nm. Therefore, do not produce unnecessary fragment and can be with impurity Remove. In addition, this kind light can easily obtain owing to use vacuum ultraviolet light modulation, and, dress The structure of putting is also simple.
In addition, in the checkout gear of chemical substance of the present invention, owing to will be higher than signal specific intensity The voltage amplitude that the impurity quality that high concentration exists is counted the SWIFT waveform of institute's respective frequencies improves, and The voltage amplitude of the part that impurity concentration is low reduces. Therefore, can optionally remove high concentration especially Impurity owing to can optionally remove impurity, the needed little energy of SWIFT can be finished. Cause This, owing to the supply unit miniaturization can be need not to use excessive power supply, so comparatively economical.
In addition, in the checkout gear of chemical substance of the present invention, the impurity big for the quality number, Provide than the big energy of energy that the little impurity of quality number is provided. In addition, in chemical substance of the present invention Checkout gear in, will diminish and the frequencies of light of the big SWIFT waveform of voltage amplitude amplitude variation along with frequency Spectrum makes the quality number when the transverse axis conversion, the voltage amplitude of average unit mass number is rough become constant Value. Therefore, the impurity big for the quality number can provide sufficient energy, is removed, in quality The ions that number is little owing to can provide its energy in needed abundant scope, can improve energy Service efficiency. In addition, because not needing excessive supply unit, also can lower setup cost.
In addition, in the checkout gear of chemical substance of the present invention, corresponding to a plurality of detected objects Use in the frequency band of material and do not give the SWIFT waveform of voltage amplitude to remove impurity. Then, A plurality of detected object chemical substances are detected simultaneously by quality analysis mechanism. Like this, because with a plurality of The detected object chemical substance detects simultaneously, can carry out the high mensuration of accuracy, also can improve burning control Accuracy.
In addition, in the checkout gear of chemical substance of the present invention, at the detection dress of above-mentioned chemical substance In putting, other possesses bigger than the ionization potential of detected object chemical substance and than this ionization potential The energy little with above-mentioned detected object chemical substance ionic dissociation energy sum offers this detected object chemistry Material is with the Ionized ionization mechanism of this detected object chemical substance. In addition, of the present inventionization Learn the checkout gear of material, in the checkout gear of above-mentioned chemical substance, above-mentioned ionization mechanism will Energy that add below the value of 4eV in this ionization potential offers above-mentioned inspection than ionization potential is high Survey the object chemical substance. The checkout gear of the chemical substance of these inventions can be with than detected object change Learn the ionization potential height of material and this ionization potential and above-mentioned detected object chemical substance ion from Separate and can offer this detected object chemical substance by the little energy of sum, with this detected object chemical substance from Sonization. Therefore, can not generate unnecessary fragment, in that do not destroy should residual detected object chemical substance Finish down the removal of impurity, can improve the detection sensitivity of quality analysis mechanism. Therefore, with above-mentionedization The action effect of learning the substance detecting apparatus generation complements each other, and further makes the inspection of quality analysis mechanism Survey sensitivity improves, and can pinpoint accuracy measure.
In addition, in the detection method of chemical substance of the present invention, when ionization, will be more right than detecting It is big and than this ionization potential and above-mentioned detected object chemical substance to resemble the ionization potential of chemical substance Ionic dissociation can offer this detected object chemical substance by the little energy of sum. Therefore, owing to do not destroy Detected object chemical substance and can ionization, in addition, the generation of unnecessary fragment is few during ionization. Cause This, do not destroy should be residual the detected object chemical substance under finish, can improve quality analysis mechanism Detection sensitivity.
In addition, in the detection method of chemical substance of the present invention, by provide the TICKLE waveform to The detected object chemical substance is with detected object chemical substance fragmentation. Therefore, even right corresponding to detecting Resembling in the frequency band of quality number of chemical substance has impurity, also can get rid of its impact, correctly measures. Knot Really, since almost all the fragment of detected object chemical substances all can be used as the mensuration of quality analysis mechanism Object can improve the detection sensitivity of quality analysis step.
In addition, the detection method of chemical substance of the present invention, can optionally remove exist preset proportion with On impurity. Therefore, compare with the situation of removing all impurity, available fewer energy can remove The impurity that goes necessity to remove. In addition, owing to can finish with a little energy, therefore can be with supply unit Miniaturization, comparatively economical.
In addition, in the detection method of chemical substance of the present invention, be that to be higher than setting signal strong with providing The voltage amplitude of the SWIFT waveform of the impurity institute respective frequencies of the signal strength signal intensity of degree improves, and will mix The voltage amplitude of the frequency of the part that matter concentration is low reduces. Therefore, owing to can optionally remove especially The impurity of high concentration is removed the needed energy of the low impurity of concentration and can be reduced. Therefore, remove impurity Needed energy seldom can be finished, in addition, owing to need not to use excessive power supply, and therefore comparatively Economical.
In addition, the detection method of chemical substance of the present invention, the impurity big for the quality number provides Than the big energy of energy that the little impurity of quality number is provided. In addition, in the inspection of chemical substance of the present invention In the survey method, will diminish and the frequency spectrum of the big SWIFT waveform of voltage amplitude amplitude variation along with frequency, When making the quality number as the transverse axis conversion, the rough steady state value that becomes of voltage amplitude of average unit mass number. Therefore, the ion big for the quality number can provide sufficient energy, is removed, and be little at the quality number Ions owing to can in needed abundant scope, provide energy, can propose high-octane use Efficient. In addition, because not needing excessive supply unit, also can lower setup cost.
In addition, the detection method of chemical substance of the present invention is corresponding to a plurality of detected object chemicals Use in the frequency band of matter and do not give the SWIFT waveform of voltage amplitude to remove impurity. Then, will A plurality of detected object chemical substances detect simultaneously by quality analysis mechanism. Like this, because with a plurality of inspections Survey the object chemical substance and detect simultaneously, can carry out the high mensuration of accuracy.
In addition, the detection method of chemical substance of the present invention is the detected object chemistry from a plurality of existence The detected object chemical substance that the quality number is little in the material begins in regular turn fragmentation. Therefore, because can be with many Individual detected object chemical substance all detects, and can improve the sensitivity of quality analysis, with pinpoint accuracy more Measure.
In addition, in the detection method of chemical substance of the present invention, the detection method of this chemical substance, Provide and contain corresponding at least 2 kinds of isotopic frequencies in the isotope of detected object chemical substance The TICKLE waveform, with in the isotope of this detected object chemical substance at least 2 kinds carry out fragmentation, For quality analysis. Like this, owing to use a plurality of isotopes in the quality analysis, even only have in the exhaust The situation that the dioxin of denier or its precursor exist also can improve the detection accuracy.
In addition, the detection method of chemical substance of the present invention is with what generate from the detected object chemical substance At least 2 kinds of objects as quality analysis in the isotope of fragment. Like this, owing to make in the quality analysis With the isotope of a plurality of fragments, so even only have the dioxin of denier or its precursor to deposit in the exhaust Situation, also can improve the detection accuracy.
In addition, the detection method of chemical substance of the present invention, in the detection method of above-mentioned chemical substance, Again before above-mentioned ion trap step, will be than the ionization potential of detected object chemical substance big and Can offer by the little energy of sum than this ionization potential and above-mentioned detected object chemical substance ionic dissociation This detected object chemical substance is with this detected object chemical substance ionization. In addition, the present invention is relevant The detection method of chemical substance, in above-mentioned ionization step, will than ionization potential high and Add the following energy of value of 4eV on this ionization potential, offer above-mentioned detected object chemicals Matter. Therefore, can not generate unnecessary fragment, because in that do not destroy should residual detected object chemicals Finish the removal of impurity under the matter, so can improve the detection sensitivity of quality analysis. Therefore, with above-mentioned The action effect that method of determining chemical produces complements each other, and more makes the detection of quality analysis mechanism Sensitivity improves, but the accuracy highland is measured.
The possibility of utilizing on the industry
Such as above mode, the checkout gear of chemical substance of the present invention and the detection method of chemical substance, Suit to detect denier dioxin contained in the exhaust of waste incineration facility etc. or its in pinpoint accuracy Use during precursor, even and heating furnace or other combustion furnaces running when the most prosperous, also can control its combustion The detection speed of detected object chemical substance is improved.

Claims (23)

1. the pick-up unit of a chemical substance is characterized by and possesses:
Will be than the ionization potential of detected object chemical substance big and offer this detected object chemical substance than the little energy of dissociation energy sum of the ion of this ionization potential and above-mentioned detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance;
To contain the ion trap mechanism that seals by the ion swarm of the Ionized above-mentioned detected object chemical substance ion of above-mentioned ionization mechanism by electric field, magnetic field and other mechanisms;
By containing the SWIFT waveform of the frequency content of removing the frequency corresponding, provide energy to remove the impurity removing mechanism of impurity for above-mentioned ion swarm with the orbit resonance frequency of above-mentioned detected object chemical substance ion; And
Measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance.
2. the pick-up unit of a chemical substance is characterized by and possesses:
Will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance;
To comprise the ion trap mechanism that seals by the ion swarm of the Ionized above-mentioned detected object chemical substance ion of above-mentioned ionization mechanism by electric field, magnetic field and other mechanisms;
By containing the SWIFT waveform of the frequency content of removing the frequency corresponding, provide energy to remove the impurity removing mechanism of impurity for above-mentioned ion swarm with the orbit resonance frequency of above-mentioned detected object chemical substance ion;
By TICKLE waveform, provide energy so that the fragmentation mechanism of the fragment ionization of detected object chemical substance for above-mentioned ion swarm corresponding to the frequency content of the orbit resonance frequency of detected object chemical substance ion; And
Measure the quality analysis mechanism of quality of the fragment of above-mentioned detected object chemical substance.
3. the pick-up unit of chemical substance as claimed in claim 1 or 2 is characterized by, and above-mentioned ionization mechanism will offer above-mentioned detected object chemical substance than ionization potential height and the energy below the value that adds 4eV on this ionization potential.
4. the pick-up unit of chemical substance as claimed in claim 1 or 2, wherein, above-mentioned ionization mechanism is the light generation mechanism that produces the following light of the above 200nm of wavelength 50nm.
5. the pick-up unit of chemical substance as claimed in claim 1 or 2, wherein, above-mentioned ionization mechanism is the vacuum ultraviolet light modulation.
6. the pick-up unit of a chemical substance is characterized by and possesses:
By electric field, magnetic field and other mechanisms, will contain the ion trap mechanism of the ion swarm sealing of Ionized detected object chemical substance ion;
The random waveform that produces the SWIFT waveform produces mechanism, the voltage amplitude of this SWIFT waveform in the pairing frequency of orbit resonance frequency of the impurity that the concentration that is higher than the signal intensity of setting signal intensity with demonstration exists wherein, the voltage amplitude in the pairing frequency band of orbit resonance frequency of the impurity that exists than the concentration that is lower than the signal intensity of setting signal intensity with demonstration is big; And
To produce above-mentioned SWIFT waveform that mechanism generated by this random waveform and offer the ion swarm that in above-mentioned ion trap mechanism, is closed, after removing above-mentioned impurity, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
7. the pick-up unit of a chemical substance is characterized by and possesses:
The ion trap mechanism that to contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
Generation is along with frequency becomes big and the random waveform generation mechanism SWIFT waveform that voltage amplitude dwindles; And
Above-mentioned SWIFT waveform is offered the ion swarm that is closed in above-mentioned ion trap mechanism, after removing above-mentioned impurity, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
8. the pick-up unit of a chemical substance is characterized by and possesses:
The ion trap mechanism that to contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
No matter based on the mass number size of removing subject molecule of SWIFT, the random waveform that all produces the SWIFT waveform with the constant distribution of voltage amplitude produces mechanism; And
Above-mentioned SWIFT waveform is offered the ion swarm that is closed in above-mentioned ion trap mechanism, after removing above-mentioned impurity, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
9. the pick-up unit of a chemical substance is characterized by and possesses:
The ion trap mechanism that to contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
The random waveform that produces the SWIFT waveform produces mechanism, and wherein this SWIFT waveform is not given voltage amplitude in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances, and gives voltage amplitude in the frequency band corresponding to the mass number of impurity;
By having TICKLE waveform, energy is provided for above-mentioned ion swarm, so that the fragmentation mechanism of the fragment ionization of above-mentioned a plurality of detected object chemical substances corresponding to a plurality of frequency contents of the orbit resonance frequency of above-mentioned a plurality of detected object chemical substances; And
Above-mentioned SWIFT waveform is offered the ion swarm that is closed in above-mentioned ion trap mechanism, after removing above-mentioned impurity, measure the quality analysis mechanism of the quality of above-mentioned detected object chemical substance or its fragment.
10. as the pick-up unit of each described chemical substance in the claim 6 to 9, also possess: will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization mechanism of this detected object chemical substance.
11. the pick-up unit of chemical substance as claimed in claim 10, wherein, above-mentioned ionization mechanism will offer above-mentioned detected object chemical substance than ionization potential height and the energy below the value that adds 4eV on this ionization potential.
12. the detection method of a chemical substance is characterized by and has:
Will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance;
By electric field, magnetic field and other mechanisms, will contain the ion trap step of the ion swarm sealing of Ionized detected object chemical substance ion;
By containing the frequency content SWIFT waveform of removing the frequency corresponding with the orbit resonance frequency of above-mentioned detected object chemical substance ion, energy is provided for above-mentioned ion swarm, remove step with the impurity of removing impurity; And
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance.
13. the detection method of a chemical substance is characterized by and has:
Will be than the ionization potential of detected object chemical substance big and littler energy than this ionization potential and above-mentioned detected object chemical substance ionic dissociation energy sum offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance;
The ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
By containing the frequency content SWIFT waveform of removing the frequency corresponding with the orbit resonance frequency of above-mentioned detected object chemical substance ion, energy is provided for above-mentioned ion swarm, remove step with the impurity of removing impurity;
By TICKLE waveform, energy is provided for above-mentioned ion swarm, so that the fragmentation step of the fragment ionization of detected object chemical substance corresponding to the frequency content of the orbit resonance frequency of detected object chemical substance ion; And
Measure the quality analysis step of quality of the fragment of above-mentioned detected object chemical substance.
14. the detection method of a chemical substance is characterized by and has:
The ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
Measure the distribution of above-mentioned ion swarm impurities, and will contain SWIFT waveform, offer above-mentioned ion swarm and remove step with the impurity of removing impurity corresponding to the frequency content that has the impurity more than the preset proportion; And
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
15. the detection method of a chemical substance is characterized by and has:
The ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms:
The SWIFT waveform is offered above-mentioned ion swarm, remove step with the impurity of removing impurity, the voltage amplitude of this SWIFT waveform in the pairing frequency of orbit resonance frequency of the impurity that the concentration that is higher than the signal intensity of setting signal intensity with demonstration exists wherein, the voltage amplitude in the pairing frequency band of orbit resonance frequency of the impurity that exists than the concentration that is lower than the signal intensity of setting signal intensity with demonstration is big; And
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
16. the detection method of a chemical substance is characterized by and has:
The ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
To become big and SWIFT waveform that voltage amplitude dwindles offers above-mentioned ion swarm along with contained frequency, remove step with the impurity of removing impurity; And
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
17. the detection method of a chemical substance is characterized by and has:
By electric field, magnetic field and other mechanisms, will contain the ion trap step of the ion swarm sealing of Ionized detected object chemical substance ion;
No matter based on the mass number size of removing subject molecule of SWIFT, the random waveform that all produces the SWIFT waveform with the constant distribution of voltage amplitude produces step; And
Above-mentioned SWIFT waveform is offered the ion swarm that is closed with after removing above-mentioned impurity in above-mentioned ion trap mechanism, measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
18. the detection method of a chemical substance is characterized by and has:
The ion trap step that will contain the ion swarm sealing of Ionized detected object chemical substance ion by electric field, magnetic field and other mechanisms;
The SWIFT waveform of voltage amplitude will be provided in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances, offer above-mentioned ion swarm, the step of residual a plurality of detected object chemical substances to remove impurity; And
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
19. the detection method of a chemical substance is characterized by and has:
To contain the ion trap step of sealing by electric field, magnetic field and other mechanisms by the ion swarm of the Ionized detected object chemical substance of above-mentioned ionization mechanism ion;
The SWIFT waveform of voltage amplitude will be provided in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances, offer above-mentioned ion swarm, to remove the step of impurity and residual a plurality of detected object chemical substances;
From above-mentioned a plurality of detected object chemical substances,, give the fragmentation step of fragmentation in regular turn from the little detected object chemical substance of mass number: and
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
20. the detection method of a chemical substance is characterized by and has:
The ion trap step of ion swarm sealing that will contain the detected object chemical substance ion of Ionized a plurality of mass number inequalities by electric field, magnetic field and other mechanisms;
The SWIFT waveform of voltage amplitude will be provided in a plurality of frequency bands corresponding to the mass number of a plurality of detected object chemical substances, offer above-mentioned ion swarm, to remove the step of impurity and residual a plurality of detected object chemical substances;
The TICKLE waveform of the corresponding frequency of at least 2 kinds of isotopes is provided in the isotope that contains with above-mentioned detected object chemical substance, with the fragmentation step of carrying out fragmentation with at least 2 kinds in the isotope of this detected object chemical substance: and
Measure the quality analysis step of the quality of above-mentioned detected object chemical substance or its fragment.
21. as the detection method of each described chemical substance in the claim 12 to 20, wherein, in above-mentioned quality analysis step, with at least 2 kinds in the isotope of the fragment that generates by the detected object chemical substance as the instrumentation object.
22. detection method as each described chemical substance in the claim 14 to 20, it is characterized by, also have: before above-mentioned ion trap step, will be than the ionization potential of detected object chemical substance big and than this ionization potential and the little energy of above-mentioned detected object chemical substance ionic dissociation energy sum, offer this detected object chemical substance, with the Ionized ionization step of this detected object chemical substance.
23. the detection method of chemical substance as claimed in claim 22, wherein, above-mentioned ionization step will offer above-mentioned detected object chemical substance than ionization potential height and the energy below the value that adds 4eV on this ionization potential.
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