WO2010059272A1 - Mesures de la mobilité ionique pour caractériser un fluide de formation - Google Patents

Mesures de la mobilité ionique pour caractériser un fluide de formation Download PDF

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WO2010059272A1
WO2010059272A1 PCT/US2009/051667 US2009051667W WO2010059272A1 WO 2010059272 A1 WO2010059272 A1 WO 2010059272A1 US 2009051667 W US2009051667 W US 2009051667W WO 2010059272 A1 WO2010059272 A1 WO 2010059272A1
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ion mobility
ion
fluid
sample
mobility device
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PCT/US2009/051667
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English (en)
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Oleg Zhdaneev
Gordon Lambertus
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Services Petroliers Schlumberger
Schlumberger Canada Limited
Schlumberger Holdings Limited
Schlumberger Technology B.V.
Prad Research And Development Ltd
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Priority to CA2744020A priority Critical patent/CA2744020A1/fr
Priority to EP09827915A priority patent/EP2347253A1/fr
Publication of WO2010059272A1 publication Critical patent/WO2010059272A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples

Definitions

  • This invention generally relates to methods and devices of chemical analysis of fluids and gases. In particular, utilizing ion mobility techniques for detecting and identifying components of interest in a fluid mixture such as in a formation fluid.
  • Ion mobility spectrometers separate ionic species based on their ion mobility in a given media (either gas or liquid).
  • Ion mobility spectrometers separate ionic species based on their ion mobility in a given media (either gas or liquid).
  • IMS time-of-flight Ion Mobility Spectrometry
  • DMS differential mobility spectrometry
  • FAMMS field asymmetric ion mobility spectrometry
  • Ion mobility measurements have been widely used for identification of components including but not limited to drugs, explosives, and chemical warfare agents [Eiceman. G.A., Karpas Z, Ion Mobility Spectrometry, CRC Press, 2005].
  • IMS time-of-flight Ion Mobility Spectrometry
  • a weak DC field gradient is established between an upstream electrode and a downstream collector electrode and then an ionized sample is released into the DC field.
  • the ionized sample flows toward the collector electrode.
  • Ion species are identified based on the time of flight of the ions to the collector.
  • the DC field is weak where ion mobility is constant.
  • the IMS spectrometers separate ions based on their steady state ion mobilities under constant electric field. More recently, improvements have been reported in the lower limits of detectibility for ion mobility instruments.
  • a typical differential mobility spectrometry (DMS) device includes a pair of opposed filter electrodes defining an analytical gap between them in a flow path (also known as a drift tube or flow channel). Ions flow into the analytical gap.
  • a compensated high-low varying asymmetric RF field (sometimes referred to as a filter field, a dispersion field or a separation field) is generated between the electrodes transverse the ion flow in the gap.
  • Field strength varies as the applied RF voltage (sometimes referred to as dispersion voltage, separation voltage, or RF voltage) and size of the gap between the electrodes.
  • ions are displaced transversely by the DMS filter field, with a given species being displaced a characteristic amount transversely toward the electrodes per cycle.
  • DC compensation is applied to the electrodes to compensate or offset the transverse displacement generated by the applied RF for a selected ion species.
  • the result is zero or near-zero net transverse displacement for that species, which enables that species to pass through the filter for downstream processing such as detection and identification.
  • Other ions undergo a net transverse displacement toward the filter electrodes and will eventually undergo collisional neutralization on one of the electrodes.
  • Both the typical DMS and IMS devices separate the ions through the use of nonlinear mobility, which occurs at high values of normalized electric field.
  • the normalized electric field refers to the relation between the applied electric field at a given location in space divided by the neutral particle number density.
  • the normalized electric field is a key parameter in ionized gases and plasmas, as the energy of ionized particles, the breakdown and sustaining voltages and other key parameters depend upon this ratio.
  • the DMS devices have sensitivity and selectivity that are still substantially worse (less) than linear drift tubes. Further, such systems typically operate at atmospheric pressure.
  • the compensation voltage applied to the filter electrodes typically generates fringe fields that force ions to impact and deposit charge along the flow path of the system adjacent to the filter. As the ions deposit their charge, a charge build up occurs that counteracts the influence of the fringe fields and allows for subsequent stable ion detection.
  • the period of time in which the DMS system reaches stable ion detection introduces response time delays, especially in a system performing multiple sample detections, which may reduce the speed and responsiveness of current DMS systems.
  • the dependence on a charge build up to enable stable ion detection may adversely affect the stability and sensitivity of the DMS system where the charge build up is dependent on other variable factors such as surrounding environmental conditions.
  • the above noted spectrometers e.g., IMS, DMS or FAIMS
  • performance is significantly limited.
  • the performance of the ion mobility spectrometers in these circumstances can be improved by increasing the temperature of the gas.
  • High temperature ion mobility spectrometers are common in applications that require high resolution analysis, such as explosive detection.
  • the use of high temperature drift tubes in differential mobility spectrometer devices results in high power consumption, limited portability and other operational disadvantages, including slow turn-on from cold conditions.
  • dry drift gas is often required in these types of spectrometers.
  • a dehumidifier in front of the unit has been used to address these problems (either as a water absorber or as a hydrophobic membrane) with significant trade-offs.
  • the volume and weight, as well as the need for regeneration, makes the use of dehumidifier cell impractical, while the use of the hydrophobic membrane decreases the volume/amount of the sample that is introduced into the device, decreases its sensitivity.
  • the invention can include a method for chemically analyzing at least one sample of fluid.
  • the method comprises the steps of: (a) directing a gas flow of the at least one fluid sample into a mixing region of an ion mobility device, wherein the mixing region is in communication with at least one container having at least one other fluid.
  • the method further includes the step of (b) creating an ion flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one sample and the at least one other fluid.
  • the method of the invention includes the step of (c) injecting the ion flow from the mixing region into at least one ion mobility assembly of the ion mobility device, the at least one ion mobility assembly comprising at least one mobility tube; and, detecting the ions from the ion flow exiting the ion mobility assembly.
  • the method can include the at least one sample of fluid that is collected from one or more inlet location where the fluids originated. Further, the method can provide for the ion mobility device having one or more sampling chamber. The at least one fluid sample may be directed into the one or more sampling chamber of the ion mobility device wherein the one or more sampling chamber provides for the at least one fluid sample to be put in a gaseous phase so as to create the gas flow of step (a).
  • the at least one device can be structured and arranged between the at least one sample chamber and the mixing region, such that the at least one device is from the group consisting of one of a separation system, a nondestructive sensor, a mass spectrometer, another ion mobility device, or some combination thereof.
  • the separation system includes one of a liquid chromatography, a gas chromatography, a size exclusion chromatography system, or some combination thereof.
  • the method can include the at least one other fluid to consist of one or more drift gas, wherein the one or more drift gas is from the group consisting of one of nitrogen, helium, air, argon, water vapor, one or more organic molecules, one or more inorganic molecules or any combination thereof.
  • the at least one sample and the at least one other fluid can be ionized from a group consisting of one of a flux of electrons from a radioactive source, by high energy photons with an energy higher than 12.8 eV, a gas discharge device, an ion flux system, a field ionization assembly, a penning ionization process, a chemical ionization assembly, a dissociative ionization assembly, a collision induced ionization assembly or some combination thereof.
  • the at least one ion mobility assembly includes a top electrode and a bottom electrode, such that ion flow is injected into a filter region of the at least one mobility tube by one of orthogonally or parallel in relation to an axis of the bottom electrode.
  • the method can include the at least one mobility tube that has a filter region comprising of two or more electrodes along with at least one inlet positioned on an end of the at least one mobility tube.
  • the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are spaced apart from each other, such that an inlet cross-section is greater than an exit cross-section.
  • the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are spaced apart from each other, such that an inlet cross-section is less than an exit cross-section.
  • the filter region may have a filter geometry wherein two electrodes of the two or more electrodes are non-uniformly spaced apart from each other, such that an inlet cross-section is greater than an exit cross-section.
  • the filter region can have a filter geometry wherein at two electrodes of the two or more electrodes are non-uniformly spaced apart from each other, such that an inlet cross- section is less than an exit cross-section.
  • the at least one mobility tube can include at least one inlet positioned between a first end and a second end of the at least one mobility tube, wherein the filter region has a filter geometry wherein two electrodes of the two or more electrodes are uniformly spaced apart from each other.
  • the method can include the at least one mobility tube having a filter region, such that the filter region is positioned downstream from step (c) or an ionization region.
  • the at least one ion mobility assembly can simultaneously detects ions of both negative and positive polarities. It is also possible that the at least one sample and the at least one other fluid are ionized, after ionization a plurality of negative and positive ions accelerate in at least two electric fields according to their respective ion polarities and are detected on opposite sides of at least one mobility tube of the plurality of mobility tubes.
  • the method can include the ion mobility device having two or more ion mobility assemblies. Further, the at least one ion mobility assembly may have two or more detectors. Further still, the at least one fluid from the fluids can be from the group consisting of one of a formation fluid mixture or a fluid from an oilfield application. It is also possible the fluids can be one of formation fluids or fluids from the mixing region or some combination thereof.
  • the formation fluids can be from a group consisting of one of water, crude oil, drilling mud, gases or any combination thereof. Futher, the fluids from the mixing region may be from the group consisting of one of gases, inorganic dopant, organic dopant, water vapor or any combination thereof.
  • the ion mobility device can be from the group consisting of one of a ion mobility spectrometry or a differential ion mobility spectrometry.
  • the method can include recording the results of the detected ions by the at least one ion mobility assembly into a processor as an ion mobility spectral profile data, and then inputting other measured data from other well log systems into the processor. Further, analyzing the combination of the ion mobility spectral profile data with the other measured data by conducting one of a quantitative analysis, a qualitative analysis or both a quantitative and qualitative analysis so as to provide reliable reservoir evaluation information for making a decision in relation to oilfield applications.
  • the invention can include a method for chemical analysis of fluids from an oilfield application such as a reservoir.
  • the method comprises of the step of (a) collecting at least one sample of fluid from one or more inlet location where the fluids originated, and an ion mobility device having one or more sampling chamber and at least one ion mobility assembly. Further, the step of (b) directing the at least one fluid sample into the one or more sampling chamber of the ion mobility device wherein the one or more sampling chamber provides for the at least one fluid sample to be put in a gaseous phase so as to create a gas flow.
  • the step of (c) directing the gas flow of the at least one fluid sample into a mixing region of the ion mobility device, wherein the mixing region is in communication with at least one container having at least one other fluid.
  • the step of (d) creating an ion flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one sample and the at least one other fluid.
  • the method includes step (e) injecting the flow from the mixing region into the at least one ion mobility assembly of the ion mobility device, the at least one ion mobility assembly comprising at least one mobility tube; and, detecting the ions from the flow exiting the at least one ion mobility assembly.
  • the invention can include a ion mobility device.
  • the ion mobility device comprises of a mixing region than can be in fluid communication with a first fluid of at least one fluid sample and one or more container having at least one other fluid, such that the first fluid can be mixed with the at least one other fluid.
  • the ion mobility device can include a source for generating a flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one fluid sample and the at least one other fluid.
  • At least one ion mobility assembly fluidly connected to the source, the at least one ion mobility assembly comprising at least one mobility tube and at least one detector, wherein the at least one ion mobility assembly is detecting ions from an ion flow exiting the ion mobility assembly.
  • the ion mobility device can include the first fluid of the at least one fluid sample that is in fluid communication with one or more sample chamber. Further, the one or more sample chamber can provide for the first fluid of the at least one fluid sample to be put in a gaseous phase so as to create a gas flow. Further still, the at least one other fluid consists of one or more drift gas, wherein the one or more drift gas is from the group consisting of one of nitrogen, helium, air, argon, water vapor, one or more organic molecules, one or more inorganic molecules or any combination thereof. It is possible, the at least one mobility tube includes a filter region comprising of two or more electrodes along with at least one inlet positioned on an end of the at least one mobility tube.
  • the ion mobility device can include the filter region having a filter geometry wherein two electrodes of the two or more electrodes are spaced apart from each other, such that an inlet cross-section is greater than an exit cross-section.
  • the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are spaced apart from each other, such that an inlet cross-section is less than an exit cross-section.
  • the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are non- uniformly spaced apart from each other, such that an inlet cross-section is greater than an exit cross-section.
  • the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are non-uniformly spaced apart from each other, such that an inlet cross-section is less than an exit cross-section.
  • the at least one mobility tube may include at least one inlet positioned between a first end and a second end of the at least one mobility tube, wherein the filter region can have a filter geometry wherein two electrodes of the two or more electrodes are uniformly spaced apart from each other.
  • the at least one mobility tube can include a filter region, such that the filter region is positioned downstream from step (c) or the ionization region.
  • the ion mobility device can include the at least one ion mobility assembly having a top electrode and a bottom electrode, such that ion flow is injected into a filter region of the at least one mobility tube by one of orthogonally or parallel in relation to an axis of the bottom electrode.
  • at least one device is structured and arranged between the at least one sample chamber and the mixing region, such that the at least one device is from the group consisting of one of a separation system, a non-destructive sensor, a mass spectrometer, another ion mobility device, or some combination thereof.
  • the separation system includes one of a liquid chromatography, a gas chromatography, a size exclusion chromatography system, or some combination thereof. It is possible, the at least one ion mobility assembly simultaneously detects ions of both negative and positive polarities.
  • the ion mobility device can have two or more ion mobility assemblies. Further, the at least one ion mobility assembly may have two or more detectors.
  • the ion mobility device can include the at least one ion mobility device to use a plurality of electrostatic fields to focus ion flux in the at least one mobility tube to effect a peaks resolution and a signal to noise ratio.
  • the at least one ion mobility device includes at least one magnetic field that is used for ion flux manipulation to improve one or more component of interests resolutions in the analyzable mixture of the first fluid with the at least one other fluid. It is possible a m-sequence ion injection can be used to enhance a signal to noise ratio and resolution between the one or more components of interests in ion mobility measurements.
  • the at least one ion mobility device can include multiplexing ion mobility spectrometry cells, such that an array of sensors are arranged in parallel rather in series, along with the at least one sample being introduced as a continuous flow to an ionization source, a filter region, and a plurality of collectors as the at least one sample is transported by means of a transfer gas.
  • ion mobility device is from the group consisting of one of a ion mobility spectrometry or differential ion mobility spectrometry. It is possible for the ion mobility device to operate above an ambient pressure.
  • the at least one ion mobility assembly can have one or more electric field, such that the one or more electric field oscilating is with one of one or more maximum pulses, one or more minimum pulses or both.
  • the invention can include a system for chemical analysis of fluids from an oilfield application such as a reservoir.
  • the system comprises of (a) collecting at least one sample of fluid from one or more inlet location where the fluids originated, and an ion mobility device having one or more sampling chamber and at least one ion mobility assembly. Then, (b) directing the at least one fluid sample into the one or more sampling chamber of the ion mobility device wherein the one or more sampling chamber provides for the at least one fluid sample to be put in a gaseous phase so as to create a gas flow.
  • (c) directing the gas flow of the at least one fluid sample into a mixing region of the ion mobility device, wherein the mixing region is in communication with at least one container having at least one other fluid. Then, (d) creating an ion flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one sample and the at least one other fluid. Finally, (e) injecting the flow from the mixing region into the at least one ion mobility assembly of the ion mobility device, the at least one ion mobility assembly comprising at least one mobility tube; and, detecting the ions from the flow exiting the at least one ion mobility assembly.
  • FIG. 1 shows reduced mobility coefficients versus mass of drifted components, wherein alcohols are representative as a square shape ( ), esters representative as a triangle shape ( ⁇ ), and organophosphates representative as a circle shape (O) (see the G.A. Eiceman Final Report, in Geocenter,
  • FIG. 2 shows a small quantity of the formation fluid extracted from a reservoir using a sampling tool (see R. J. Schroeder and J. A. Tarvin, US Patent
  • FIG. 3 shows the use of an ion mobility spectrometer to simultaneously detect ions of both polarities, according to embodiments of the invention;
  • FIG. 4 shows at least one embodiment to increase ion flux density, according to embodiments of the invention;
  • FIG. 5 shows at least one embodiment that can increase ion flux density as well as looks to avoid strong ion repulsion when ion density increases in the center of the drift tube, according to embodiments of the invention;
  • FIG. 6 shows at least one embodiment that addresses the utilization of M- sequence for ion-mobility measurements, according to embodiments of the invention; [0030] FIG.
  • FIG. 7 shows when changing the Ionization Chemistry at least one method of the invention can include changing the selectivity of the DMS by controlling the ionization process, according to embodiments of the invention;
  • FIG. 8 shows that by changing the ionization source (higher energy) or the operating conditions of the DMS it is possible to induce fragmentation in many sample species, according to embodiments of the invention;
  • FIG. 9 shows a waveform describing an alternating electric field in DMS according to embodiments of the invention;
  • FIG. 10 shows a waveform describing a higher order alternating electric field, according to embodiments of the invention;
  • FIG. 11 shows Contour plots for 3-methyl-2-butanone and benzene for RF voltages of 800 V (a), 900 V (b), 1000 V (c), 1100 V (d), 1200 V (e), 1300
  • FIG. 12 shows at least one conceptual image of multiplexed DMS, according to embodiments of the invention.
  • the invention can include a method for chemically analyzing at least one sample of fluid.
  • the method comprises the steps of: (a) directing a gas flow of the at least one fluid sample into a mixing region of an ion mobility device, wherein the mixing region is in communication with at least one container having at least one other fluid.
  • the method further includes the step of (b) creating an ion flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one sample and the at least one other fluid.
  • the method of the invention includes the step of (c) injecting the ion flow from the mixing region into at least one ion mobility assembly of the ion mobility device, the at least one ion mobility assembly comprising at least one mobility tube; and, detecting the ions from the ion flow exiting the ion mobility assembly.
  • the invention can include a ion mobility device.
  • the ion mobility device comprises of a mixing region than can be in fluid communication with a first fluid of at least one fluid sample and one or more container having at least one other fluid, such that the first fluid can be mixed with the at least one other fluid.
  • the ion mobility device can include a source for generating a flow of gaseous ions, a mixture of gaseous ions or a gaseous neutral species from the at least one fluid sample and the at least one other fluid.
  • At least one ion mobility assembly fluidly connected to the source, the at least one ion mobility assembly comprising at least one mobility tube and at least one detector, wherein the at least one ion mobility assembly is detecting ions from an ion flow exiting the ion mobility assembly.
  • the invention includes methods and devices for disclosing a novel approach for chemical composition analysis of formation fluids in a downhole/surface environment, including but not limited to the light hydrocarbons (gases), H 2 s, and others.
  • the present embodiments of the invention are not limited to subterranean environments but may also include surface environments.
  • the embodiments of the invention utilize the ion mobility technique for mixture analysis.
  • Embodiments of the invention consist of two parts, hardware embodiments along with methods of measurements.
  • the hardware components may consist of a sampling system, an ionization chamber, an electrical field generator, a magnetic field generator, a drift chamber, at least one detector, a pre-separation device, a gas supply system, among other things.
  • the operating software can include at least one algorithm and database to quantitatively identify components in the mixture.
  • the invention methods and devices can be capable of real-time formation fluids characterization at downhole conditions, and could be implemented on different platforms (wireline, logging while drilling, testing, etc) utilizing different types of conveyance (wireline cable, drilling tubing, coil tubing, tractor). It is also noted that along with downhole conditions, surface conditions can also be considered. Further, the invention the methods and devices can be an improvement over conventional methods that require samples to be brought to surface facilities for analysis and/or limited to optical spectroscopy. The data obtained by at least one embodiment of the invention could be combined with other logging data like gas chromatography, optical measurements, and mass spectrometry.
  • Embodiments of the invention can utilize chemical and electron ionization from different sources.
  • Time-of-flight Ion Mobility Spectrometry (IMS) and differential mobility spectrometry (DMS) provide for selective marker-free identification of molecules and molecular aggregates in a mixture that can be used as a detector for gas/liquid chromatography and other compositional analysis systems like a mass spectrometry.
  • Embodiments of this invention may also be coupled with a pre-separation apparatus such as GC or LC as well as with a device for accurate component identification like MS.
  • a pre-separation apparatus such as GC or LC
  • MS device for accurate component identification like MS.
  • the ion mobility spectrometers could be combined in a tandem like IMS-IMS, IMS-DMS and so on.
  • a mobility spectrum can contain all the information provided by a mobility measurement. This includes the mobility coefficients (characteristic of an ion), peak shape (characteristic of the drift tube), and ion fragmentation (characteristic of a chemical class). Mobility coefficients are governed by size to charge ratio and the reduced mass of the ion in the atmosphere of analysis and could be used for the identification of the components of interest (see for example table 1 below and FIG. 1) especially in combination with gas chromatography (GC), liquid chromatography (LC), and mass spectrometry (MS).
  • GC gas chromatography
  • LC liquid chromatography
  • MS mass spectrometry
  • the Sionex DMS is a microfabricated detector with electrode dimensions of 15 mm x 1.5 mm with a gap of 0.5 mm. When housed with an onboard EPC and electronics the whole unit is just about 4-in wide by 6-in long by 2-in high. Table 1
  • Table 1 illustrates example of mobility coefficients obtained experimentally [Eiceman, G.A., Final Report, Geocentersjnc, Subcontract GC -2192 -91-002, Prime contract DAAAl 5-90-C-1006, August 10, 1993]
  • Spectrometry techniques currently implemented in formation fluid analysis have a limited ability to resolve the presence of different components in a complex mixture. For example, when utilizing ion mobility spectrometry it is possible to distinguish between the components in the formation mixture, and then separate and identify them with a proper spectral library. It is also noted that implementation of ion mobility methods of analysis could significantly improve the logging while drilling measurements due to the extremely fast response of these measurements. This could be utilized for identification of components of interest while drilling (e.g. methane). [0045] The components of ion mobility analysis system can be grouped into several main categories:
  • the invention methods and devices describe at least one implementation of mobility spectrometry for downhole formation fluid analysis and or for surface fluid analysis.
  • a small quantity of the formation fluid is extracted from a reservoir using a sampling tool [Schroeder, R. J., Tarvin, J. A., Apparatus and Method for Analyzing the Composition of Formation Fluids, US Patent 5166747 (1992).].
  • the formation fluid after preliminary filtering e.g. to remove sand particles via a sampling tool flowline, is delivered to the module where an ion mobility spectrometer is placed.
  • the liquid or gas is allowed to expand and evaporate in a sample chamber that is roughly one million times the volume of the extracted fluid.
  • a valve e.g. a piezo-electric leak valve
  • the sample gases are ionized either by photons, electrons, ions, or by interaction with exited reactant particles.
  • the molecular ions or fragments travel into the drift chamber under an electrical field gradient where they are separated on the basis of their mobility coefficients. After separation in the drift chamber the ions reach the detector, which can consist of a Faraday cup.
  • a differential mobility spectrometry consists of nominally the same components as the ion mobility spectrometer previously described, i.e. an ionization source, a drift tube region, detectors, signal analyzers, and the interface software.
  • a sample will be introduced as a continuous flow to the ionization source, the filter region, and the collectors as it is transported by means of a transfer gas.
  • K is the mobility coefficient, and varies as a square root of electric field in case of strong fields.
  • q is the ion charge
  • N is the density of the drift gas
  • m is the ion mass
  • M is the mass of the neutral particle
  • k is the Boltzmann constant
  • T is the temperature of the drift gas
  • ⁇ is the collision cross-section of the ion neutral particle ( « ⁇ - d 2 , where d is the sum of the ion and neutral particle radii).
  • the drift gas determines the sort of reagent ion and complex formation that will be produced in the ionization part of the device. Omitting the plasma chemical interaction in the ionization part of the device the effect of the drift gas on ion mobility can be evaluated quantitatively. For small ions near room temperature the mobility could be expressed using the following equation [Revercomb H.E.; Mason, E. A. "Theory of Plasma Chromatography/Gaseous Electrophoresis: A Review", Anal. Chem. 1975, 47, 970-983]:
  • Table 2 illustrates some quantitative evaluation of effects of drift gas change.
  • H + (H 2 O) is the reactant ion
  • MH + (H 2 O) is the
  • O 2 - (H 2 O) n is the negative reactant ion
  • MO 2 - (H 2 O) n is the negative product ion
  • the sample and drift gas are ionized either by a flux of electrons from a radioactive source (e.g. Ni 63 ) or by high energy photons (energy higher than 12.8 eV which is the ionization potential for CH 4 ). After ionization the negative and positive ions accelerate in the electric fields according to their polarities and are detected on opposite sides of the drift tube.
  • a radioactive source e.g. Ni 63
  • high energy photons energy higher than 12.8 eV which is the ionization potential for CH 4
  • the ion beam is shifted from the center of the drift tube (e.g. using ion optics) to increase signal-to-noise ratio.
  • At least one embodiment of the invention proposes to address the utilization of M-sequence for ion-mobility measurements, for example the M-sequence [P.Z. Marmarelis and V.Z. Marmarelis, Analysis of physiological systems, Plenum Press, New York/London, 1978] can be used to improve signal-to-noise ratio (SNR) of ion mobility measurements.
  • An M-sequence is a pseudo-random sequence of pulses a, that assumes L different values, where L is the level of the sequence. In the example, L equal to 2 will be considered. Thus, the M-sequence will only assume two different values (1 and -1), as shown in FIG. 6.
  • An auto-correlation function of M- sequence has a sharp peak:
  • M-sequence is orthogonal to the noise. It means that utilization of M-sequence increases the SNR level. If multiple copies of an M-sequence of duration ⁇ are injected continuously into a drift tube (e.g.
  • the detected signal will correspond to the injected sequence, circularly permuted by an amount equal to the drift time t d between ion injector and ion detector.
  • the cross- correlation function between the injected signal and the detected signal will peak sharply at t d , thus allowing for precise measurement of the drift time.
  • the magnetic sector mass spectrometer is one of the earliest mass spectrometer developed for component identification [C Brunnee, The ideal mass analyzer: fact of fiction?, International Journal of Mass Spectrometry and Ion Processes, 76 (1987), 125-237].
  • the utilization of a magnetic field provides for an additional mechanism that could be used for ion flux manipulation and improving the quality of analysis, for example increasing peak resolution.
  • the implementation of a magnetic field will help to focus ions as well.
  • the Lorentz describes the effect of magnetic field on ion flux in the drift tube:
  • At least one method of ionization includes the method of differential ion mobility spectrometry (DMS).
  • DMS can utilize a variety of ionization sources including radioactive ionization, corona discharge ionization, capacitive discharge ionization, and UV photo-ionization (the most common being 63 Ni). Both positive and negative reactant ions react through proton transfer and charge transfer to generate analyte ions.
  • the reactant ion pool in the case of DMS is largely composed of proton-water-nitrogen clusters for the positive ions, and oxygen anion- water clusters for the negative ions (Eiceman, G, Karpas, Z.
  • At least one method can include changing the selectivity of the DMS by controlling the ionization process.
  • the process of atmospheric pressure chemical ionization is still largely not understood within the science arena. It has, however, been demonstrated that by biasing the ionization towards a certain species, more accurate measurements of a specific species in a complex matrix can be achieved ⁇ Lawrence, A. H., Neudorfl, P.
  • ion mobility can be governed similarly to that which was explained above for IMS. Most commonly a single drift gas can be used to transport ions through the filter region of a DMS. Changing the mobility of an ion in the field can be manipulated using equation 2 (see above). Depending on how the mobility of specific ions change, the transport gas, or a mixture of gases can be used to isolate those ions for detection.
  • Negative ion detection in DMS is most often a result of fragmentation of the parent molecule to yield a halogen ion.
  • the negatively charged species traverse the ion filter region in the same manner as positive ions and reach a biased collector plate.
  • the most common ion sources in IMS/DMS are the 63 Ni and a photoionization source (UV lamp).
  • UV lamp photoionization source
  • the electron energy can fragment a halide ion resulting in the formation of both positive and a negative daughter species.
  • the negative daughter species is the fragmented halogen ion.
  • fragmentation can be particularly useful. In these cases the fragmented species most likely would have significantly higher mobilites (than the parent ions) and the separation and detection of these fragments relative to other parent ions will be much simpler.
  • the fragmentation of the parent ions then provides several avenues for exploitation of the mobility data. Fragmentation patterns collected during an analysis can be matched to libraries for component identification similar to mass spectral databases. Furthermore, the presence of a specific daughter ion can be used as an indicator of the parent molecule structure, and this type of information can aid in characterization of mixture constituents.
  • DMS- DMS techniques analogous to MS-MS techniques, can be used for structural identification of unknown components (Kendler, S., Lambertus, G. R., Dunietz, B. D., Coy, S. L., Nazarov, E. G, Miller, R. A., Sacks, R. A., "Fragmentation patterns and mechanisms of aromatic compounds in atmospheric pressure studied by GC-DMS and DMS-MS, " Int. J. of Mass, Spectrom. 2007, 263, 137-147).
  • the invention addresses the variation in the high-frequency field, for example, the electric field in DMS can be generated by applying a high frequency RF voltage and a low DC voltage to two parallel plate electrodes.
  • the invention provides for a simplified waveform as shown in FIG. 9, where the maximum field strength, E ma ⁇ , is less than 10000 V/cm, and the minimum field strength, E 101n , is much less than E max .
  • t ⁇ is the portion of the period where the high field is applied
  • t 2 is the portion where the low field is applied
  • ⁇ is a constant corresponding to the area under the curve.
  • Ions in the tunable ion filter region of the DMS experience this alternating electric field and oscillate orthogonal to the direction of carrier gas flow.
  • the ion velocity in the transverse direction is described by equation 1 :
  • K is the mobility of the ion and E is the electric field strength.
  • E is the electric field strength.
  • the mobility of the ion depends on the electric field according to:
  • K(E) K 0 (O) [l + ⁇ 2 (E/ N) 2 + ⁇ 4 (E/ N ⁇ + ⁇ 6 (E/N) 6 + ... Eq.
  • N is the density of the carrier gas
  • ⁇ n indicates a coefficient in a series expansion.
  • IMS separations are done under conditions with zero field mobility in the _y-direction, and only the .STo(O) term plays a role.
  • the higher order terms (EIN) 2 and (EINf in the equation become more significant. Ion displacement from the original position can't then be measured as:
  • At is the length of time the field is applied. After substation displacement of the ion over a single RF cycle can be calculated as
  • the displacement of each ion will be different relative to the case with only a single E max and E 101n due to resulting changes in ion mobility during each portion of the RF cycle.
  • the RF cycle can be manipulated until that ion has a unique mobility. Selected mobility monitoring will then allow for the best signal to noise measurement of that ion.
  • RF cycles There are infinite combinations of RF cycles that can be employed.
  • DMS-DMS instruments can be employed where each successive DMS has a different RF cycle to generate complimentary information to describe a specific ion.
  • the invention provides for a method for programming the electric field.
  • FIG. 11 illustrates the resolution in terms of the separation space along the compensation voltage axis of a differential mobility spectrometer has been previously measured through analogy to peak capacity measurements in gas chromatography (L ⁇ mbertus, G. R., Fix, C. S., Reidy, S. M., Miller, R .A., Wheeler, D., N ⁇ z ⁇ rov, E., Sacks, R. D. "Silicon Microfabricated Column with Microfabricated Differential Mobility Spectrometer for GC Analysis of Volatile Organic Compounds, " Analytical Chemistry, 2005, 77(23), 7563-7571).
  • the invention can reduce gas consumption.
  • gas consumption is traditionally considered a problem when utilized outside the laboratory due to its portability and usage in difficult environments, e.g., in the field.
  • transport gas consumption in DMS systems is approximately on the order of 250-400 mL/min of clean dry gas.
  • This amount of consumable gas is problem in the field and/or downhole environments where transporting of such consumables is complex and expensive.
  • Re-circulating pumps and filters have been explored as a possible alternative to the high cost of transporting gas, but the issue of replacing filters then arises.
  • there is at least one other possible method of reducing transport gas consumption which may include for example, reducing the length of the ion filter region.
  • the carrier gas consumption is set out of necessity in an effort to reduce ion residence time in the ion filter region. Restricting transport gas consumption, residence time of ions in this region will increase, the alternating electric field would result in all ions hitting the electrodes and being neutralized. Further, the balance in transport gas flow also requires that molecules spend enough time in the ionization region that a good portion of them are ionized, so the balance is ionization versus neutralization. [0072] According to another aspect of the invention, the invention can alleviate some of the gas consumption problems as noted above by changing the geometry of the electrodes. For example, by shortening the length of the electrodes, a decrease in volumetric flow rate will maintain the residence time requirements in the filter region.
  • Another aspect of the invention includes multiplexed or arrayed DMS as shown in FIG. 12.
  • differential mobility spectrometers operating in scanning modes are often limited to relatively slow sampling rates, limited by step settling times when the compensation voltage is changed.
  • the ability to scan a range of alternating field strengths would help to enhance resolution along the compensation voltage axis. This works by providing conditions at which ions mobility will shift independently of other ions (present in the ion filter region at the same time) in such a manner that independent detection is possible.
  • Multiplexed DMS offers a possible to solution to both problems. A possible configuration would most simplistically consist of two or more DMS units connected end to end, where effluent from the first cell flows into the second, as shown in FIG. 12.
  • Such an arrangement of spectrometric detectors would allow for each successive filter to have different compensation voltage settings, different compensation voltage scan ranges, different field strengths, different field strength scan ranges, or can have the same settings but be used to improve the time resolution of the measurements.
  • a configuration where different ion sources are used is another implementation where selective ionization and detection can take place in several steps enhancing data output from a single measurement.
  • This invention may also be coupled with a pre- separation apparatus such as GC or LC as well as with a device for accurate component identification like MS. Further, it is also possible to improve the ion separation, such that the ion mobility spectrometers could be combined in a tandem like IMS-IMS, IMS-DMS and so on. Further, the invention has been described with reference to particular preferred embodiments, but variations within the spirit and scope of the invention will occur to those skilled in the art. It is noted that the foregoing examples have been provided merely for the purpose of explanation and are in no way to be construed as limiting of the present invention.

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Abstract

L'invention concerne des procédés et des appareils correspondants pour effectuer l'analyse chimique d'au moins un échantillon de fluide, de sorte qu'un écoulement gazeux d'au moins un échantillon fluidique est dirigé sur une région de mélange de dispositif de mobilité ionique. La région de mélange est en communication avec au moins un récipient contenant au moins un autre fluide. L'invention concerne également la création d'un écoulement d'ions gazeux, d'un mélange d'ions gazeux ou d'espèces gazeuses neutres provenant d'au moins un échantillon et d'au moins un autre fluide. L'invention concerne également l'injection de l'écoulement ionique provenant de la région de mélange dans au moins un ensemble de mobilité ionique du dispositif de mobilité ionique, ledit ensemble comprenant au moins un tube de mobilité ; et la détection des ions de l'écoulement ionique sortant de l'ensemble de mobilité ionique.
PCT/US2009/051667 2008-11-21 2009-07-24 Mesures de la mobilité ionique pour caractériser un fluide de formation WO2010059272A1 (fr)

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