# Patent

## Title
Multi-stage injector for fluid analysis

## Abstract

The present invention generally recites a method, system and apparatus for fluid analysis and more specifically recites a method system and apparatus for multistage injection of a fluid to be analyzed into a fluid analysis instrument.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority from co-pending commonly assigned U.S. Provisional Application Ser. No. 61/015,317 filed Dec. 20, 2007.
FIELD OF THE INVENTION
The present invention generally relates to the field of fluid analysis, and more particularly to a multi-stage injector for use in fluid analysis in a variety of operating environments.
BACKGROUND OF THE INVENTION
State of the Art
Gas Chromatography (GC), as described by Pilkington et al. (U.S. Pat. No. 4,739,654) or Storm and Richardson (WO 01/73424 A1) for example, provides a means for analyzing various gas-phase components of an injected sample. Using conventional GC techniques, liquid samples are introduced into the chromatograph by a variety of methods. One method is to use a syringe operated by an auto-sampler or physically manipulated by a user. In this case, the fluid inside the syringe is inserted into the GC through a septum, and is further introduced into a vaporization chamber through which carrier phase is continuously flowing. The carrier phase transports the evaporated sample onto the chromatographic column. An alternative approach may utilize a sampling valve, which takes a known volume of sample trapped in a cavity, and inserts it into a continuous stream of carrier phase. This can be performed with gas or liquid sample, in the latter case this known volume is then swept into a vaporization chamber.
Sampling valves are generally preferable for remote applications and when directly sampling environmental fluids, because they are more easily integrated into flow lines and other such sample reservoirs than syringe-based injection systems. In addition, when injecting high pressure samples, syringes have the potential for leaking sample through the end of the needle, further reducing their applicability in many scenarios.
Using either of these approaches, liquid samples are generally quickly evaporated and pushed into a chromatographic column by the carrier phase. In either of these methods, the inherent pressure of the sample is nearly atmospheric. The pressure of the carrier phase in the GC inlet device is typically less than about 150 psi.
In most existing applications and column arrangements, the volume of the evaporated sample in the carrier phase is generally too large for most columns as it would result in significant reductions in chromatographic performance (i.e. the extra-column band broadening contribution from the injection process is much larger than the on-column band broadening). As set forth previously, existing chromatographic columns typically operate at near ambient temperatures and pressures. When operating in an environment such as this, it is important to consider that a 5.0 μL liquid sample of n-octane at room temperature and pressure will evaporate into a plug of 836 μL of vapor at room temperature and pressure.
Normally, a standard capillary column expects a gas-phase injection plug of the order of 5 μL or less. Modem high speed GC using micro-bore columns, and MEMS columns, may further require an injection plug of the order of 0.1 μL or smaller. This means that it is often necessary to reduce the volume of evaporated sample volume by a factor of 1000 or even more. Traditional techniques using a split-less injector, namely an injector which introduces the entire evaporated sample directly onto the column, are therefore not desirable, from a chromatographic resolution point of view. Existing techniques have therefore introduced the use of a split injector, which allows only a small portion of the flow to enter the column, therefore reducing the volume of the gas-phase injection plug. Using a split injector, two flow paths are provided for the evaporated sample contained in the carrier phase; one with high flow resistance leading to the column, and another with low flow resistance leading to a waste line. The ratio of the two resistances determines the split ratio, which traditionally is of the order of 1:10-1:100, but easily may exceed 1:1000 with micro-bore and MEMS columns. While split injectors can work appropriately for samples at ambient temperature and pressure, liquid samples containing dissolved gases, that are at a high temperature and a high pressure and evaporate into a large plug require a significantly larger split ratio. A split this large, however, requires in turn a large increase in carrier phase in order to supply the large volume of vented flow, which is a tremendous problem in remote applications.
Furthermore, inherent in existing split injections is a difficulty in obtaining accurate quantitative analysis due to the possibility of small fluctuations in split ratio due to limited pressure and flow control reproducibility as well as variations in the evaporation process Grob, K.; Biedermann, M.; Anal. Chem. 2002, 74, 10-16 and Grob, K.; Biedermann, M.; J. Chrom. A. 2000, 897, 247-258. Existing techniques typically use an internal standard to avoid these errors. However, for remote applications such as a remote wellsite or downhole environment, incorporating an internal standard would be very difficult.
Additional existing approaches further seek to reduce the evaporated volume by reducing the volume of the liquid sample. However this has the possibility of amplifying small errors such as those due to residual contaminants on the walls of the injection cavity because of the increased surface area to volume ratio. Also, a smaller sample cavity is more prone to clogging because of particles and bubbles in the sample flow. For these reasons, a sub-microliter liquid injection is typically less desirable.
A problem of chromatography, not addressed by Pilkington et al. or Storm and Richardson is the insertion of a high temperature, high-pressure sample into the chromatographic column, an essential requirement in certain applications. In one embodiment, this high pressure sample may be a liquid sample. For example, inside an oil well ambient temperatures can be 40-200° C. or higher and the formation fluid could be at a pressure of 500-30,000 psi or higher. Introduction of a liquid sample that is at a high temperature and a high pressure of the same volume, particularly one that contains dissolved gases, that is heated and depressurized will evaporate into an even larger plug as compared to a sample at ambient conditions.
In view of the above, a novel method, system and apparatus for providing a multi-stage liquid injection to a fluid analysis device are required.
SUMMARY OF THE INVENTION
The present invention recites a multi-stage injector method and apparatus for fluid analysis. The multi-stage injector includes at least one pressure regulation stage such that the at least one pressure regulation stage regulates a fluid sample from a first pressure to a second pressure. The pressure regulation stage may regulate a high first pressure to low second pressure, or may regulate a low first pressure to high second pressure. Additionally, the pressure regulation stage may further include a mobile phase pathway for transmission of a carrier fluid (gas, liquid, or supercritical fluid), wherein the mobile phase is at a lower pressure than the first pressure (i.e. depressurization), or the mobile phase is at a higher pressure than the first pressure (i.e. pressurization). In accordance with one embodiment of the present invention, the pressure regulation stage may be a multi-port rotary valve. Additionally, the pressure regulation stage may be pressure compensated for use in an appropriate environment.
The use of the term pressure regulation for the purposes of this patent is intended to not be limited to the industrial nomenclature related to a device that controls fluid pressure. We include in our use of the term pressure regulation the ability to isolate at least one fluidic zone of a system from at least one other pressure zone within and/or outside of the system. Indeed, a device for controlling fluid pressure (e.g. “pressure regulator”) is not necessary for many embodiments of this invention.
Associated with the pressure regulation stage is at least one conditioning stage such that the conditioning stage is configured to receive the fluid sample from the pressure regulation stage. In accordance with one embodiment of the present invention, the conditioning stage may be a vaporization stage capable of vaporizing an entire fluid sample or at least a portion of a fluid sample. In one embodiment, should only a portion of the sample be vaporized the remainder of the sample may be returned to waste, or allowed to remain immobilized in some fashion within or nearby the conditioning stage. In one embodiment of the present invention, the conditioning stage may further comprise a vaporization heater. In accordance with an embodiment of the present invention, the conditioning stage may be an expansion chamber capable of providing an increase in the volume of the sample. Further associated with the expansion chamber may be a distributor to increase surface area of the sample. In an alternative embodiment of the present invention, the conditioning stage may be a compression chamber capable of providing a volume decrease of a provided sample. Further associated with the conditioning stage may be a temperature modulation mechanism capable of maintaining a fixed temperature of the conditioning stage, capable of providing a predetermined temperature ramp, or some combination thereof. In an additional embodiment of the present invention, the conditioning stage may further comprise a sample pre-selector, capable of selectively allowing specific components of the sample to evaporate and others to not evaporate or condense
Additionally, at least one injection stage is further associated with the conditioning stage, such that this injection stage provides at least a portion of said fluid sample to a fluid sample analysis instrument. In one embodiment of the present invention, the injection stage is capable of delivering a small sharp plug to a fluid analysis instrument. In one embodiment, the injection stage may provide multiple aliquots of sample (i.e. injections) to one or multiple fluid analysis instruments. These aliquots may be of identical or different compositions depending on the conditioning stage such that repeat analyses can be performed on a single analytical system for averaging or other such purposes or multiple analyses can be performed with multiple analytical systems to increase knowledge gained about the sample. In accordance with an embodiment of the present invention, the multi-stage injector method and apparatus may further be pressure compensated. In accordance with one embodiment of the present invention, the injection stage may be in communication with a fluid sample analysis instrument such as at least one chromatographic column and associated detector. In an alternative embodiment, the injection stage may be in communication with a parallel arrangement of chromatographic columns and detectors. Alternatively, the injection stage may be in communication with a variety of other fluid sample analysis instruments such as at least one of a high performance liquid chromatography system (HPLC), a supercritical fluid chromatography (SFC), size exclusion chromatography (SEC) also known as gel permeation chromatography (GPC), hyphenated methods such as LC-GC, and/or a chemical sensor, etc. as understood by one skilled in the art. Additionally, the present invention may be utilized for injecting a sample into multiple column GC systems, including multidimensional gas chromatographs, as well other analytical tools requiring a gaseous sample such as a mass spectrometer (MS), ion mobility spectrometer (IMS), or differential mobility spectrometer (DMS). Furthermore, in accordance with one embodiment of the present invention two or more injection stages may be associated with the conditioning stage. Additionally in accordance with one embodiment of the present invention the injection stage delivers a small sharp plug to an associated fluid analysis device. Furthermore, at least one of the pressure regulation stage, condition stage and/or injection stage may be pressure compensated and additionally in accordance with one embodiment the steps of pressure regulation and sample conditioning may occur substantially simultaneously.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of an embodiment of a multi-stage injector in accordance with the present invention.
FIGS. 2A-2C illustrate the concentration distribution exiting a conditioning stage of a multistage injector system for the gas-phase portions of a four-component liquid mixture being injected into a gas-phase analytical system
FIG. 3 is an alternate embodiment of the present invention using two rotary valves.
FIG. 4A is an alternate embodiment of the present invention using a solenoid valve.
FIG. 4B is a detailed view of the fluid pathway of FIG. 3A in an un-actuated state.
FIG. 4C is a detailed view of the fluid pathway of FIG. 3A in an actuated state.
FIG. 5 is a flowchart illustrating the steps necessary in practicing one embodiment of the present invention.



DETAILED DESCRIPTION OF THE INVENTION
As understood by one skilled in the art, a need for providing a sample of a fluid to a fluid analysis instrument is necessary in view of the limitations of the prior art. This fluid may be, prior to its analysis, at a high pressure. Analysis of a high pressure fluid such as this is not addressed by Pilkington et al. (U.S. Pat. No. 4,739,654) or Storm and Richardson (WO 01/73424 A1). Furthermore, the inherent problems of fluid sampling are compounded when the fluid to be analyzed is at an elevated temperature. Again, the prior art of record fails to address fluids such as these. In accordance with one potential fluid analysis application, a fluid inside an oil well (hereinafter a formation fluid) may be at 40-200° C. or higher and the formation fluid could be at a pressure of 500-30,000 psi or higher. Additionally, existing techniques fail to address the inherent concerns relating to injection volumes recited earlier. Furthermore, several fluid analysis techniques, including GC techniques, are normally performed on a sample which is at or near atmospheric pressure. Therefore it would be advantageous to lower the pressure of the fluid sample in a manner that does not compromise the fluid analysis technique to be utilized or the composition of the sample itself.
In accordance with one embodiment of the present invention, a multi-stage injector is herein recited which overcomes the shortcomings of the prior art and is patentable distinguishable over the prior art.
The multi-stage injector of the present invention includes at least one pressure regulation stage. In accordance with alternative embodiments of the present invention, multiple pressure stages may be utilized. Additionally, the present invention further utilizes at least one conditioning stage in communication with the aforementioned pressure regulation stage. This conditioning stage may be a vaporization stage wherein a known quantity of sampled high-pressure fluid is depressurized and/or evaporated. In accordance with at least one embodiment, vaporization is necessary if the sample contains liquid as existing fluid analysis techniques understood by one skilled in the art, including the use of a GC column, are performed on a sample in gas phase. In accordance with one embodiment of the present invention, the vaporization and depressurization process may be performed substantially simultaneously on a fluid sample in a chamber that includes a distribution medium, such as glass wool, which provides a large surface area and low thermal mass on which the sampled fluid is evaporated. Furthermore, in one embodiment of the present invention, this process is performed within a stream of carrier phase such as helium, hydrogen, nitrogen, air, neon, argon or other inert gas. Associated with the conditioning (or vaporization) stage of the present embodiment may be at least one injection stage capable of providing at least a portion of the fluid sample to a fluid analysis instrument.
For the purpose of clarity in describing the present embodiment, the term “formation fluid” will be used in describing the fluid sample to be analyzed. One skilled in the art will readily recognize that the present invention is not limited in use to formation fluids. Therefore, the use of the term “formation fluid” is not intended to be limiting in scope and is used exclusively for clarity in describing the present invention.
FIG. 1 illustrates an embodiment of a multi-stage injector in accordance with the present invention. In the current orientation of the multi-stage injector 10, a formation fluid may enter the multi-stage injector 10 at the fluid inlet 11 of Port A. The formation fluid, as noted previously, may be at a high pressure and a high temperature. As understood by one skilled in the appropriate art, the formation fluid may be at approximately 20,000 psi. Formation fluid entering the fluid inlet 11 of port A flows through a first cavity 14. This first cavity 14 may be of an accurately known, small volume. In accordance with one embodiment of the present invention, the first cavity 14 may be on the order of approximately 1 micro-liter. Fluid flowing through the first cavity 14 may then exit the multi-stage injector 10 via the fluid outlet 12.
Additionally, a carrier phase may further be delivered to the multi-stage injector 10 via carrier phase inlet 16 of Port B. As understood by one skilled in the art, the carrier phase may consist of numerous gases, including inert gases such as argon or helium. In one embodiment of the present invention, the carrier phase introduced to the multi-stage injector 10 at carrier phase inlet 16 is at a pressure lower than the pressure of the formation fluid introduced at the fluid inlet 11. In an alternative embodiment, the carrier phase inlet 16 may be at a pressure higher than the fluid inlet 11. In one embodiment of the present invention, the carrier phase delivered at the carrier phase inlet 16 may be at near atmospheric pressure. As seen in FIG. 1, the carrier phase passes through a second cavity 18 prior to introduction to a conditioning stage 20. In accordance with one embodiment of the present invention, the first cavity 14 and the second cavity 16 may have substantially similar volumes.
In the multi-stage injector of the present embodiment the first and second cavity (14, 18), and the conditioning stage 20 are permitted to rotate about the indicated centerline 50. For the purpose of clarity in describing the present embodiment, the first and second cavity (14, 18) and the conditioning stage 20 shall be referred to as the rotor 30. The fluid inlet 11, fluid outlet 12, carrier phase inlet 16 shall be referred to as the stator (40). The stator 40 may further include, but is not limited to, an injector output 60, or a split waste output 62.
In the illustrated embodiment, the rotor 30 is free to rotate about the centerline 50, while the stator 40 remains fixed. One skilled in the art will readily recognize that such a description of rotor 30 and stator 40 is not explicitly required, and numerous alternative arrangements may be practiced. It is fully anticipated that these numerous alternative arrangements are within the scope of the present inventive concept. In view of this, the arrangement recited herein is not intended to be limiting in scope. Rotation of the rotor 30 may be accomplished via numerous means, including the use of an external actuation device (not shown). Suitable external actuation devices include electromagnetic devices, hydraulic devices, or pneumatic devices capable of imparting a rotation of the rotor 30.
In the multi-stage injector 10 recited herein, numerous seals (not shown) are required to provide a sealed pathway for the formation fluid and the carrier phase, especially considering the anticipated rotation of the rotor 30 relative to the stator 40. For example, one or more seals may be located at the interface between rotor 30 and stator 40 to provide for reduced leakage across the fluid inlet 11, fluid outlet 12, and carrier phase inlet 14 at the junction between rotor 30 and stator 40. Some of the seals may see a differential pressure of 20,000 psi or even higher based upon the pressure differential between the fluid inlet 11 and the carrier phase inlet 16. One skilled in the art will recognize that seals (not shown) under such conditions have a high potential of developing some leakage. The leakage would be further compounded when these seals are placed in a high pressure, high temperature environment. One such environment is a borehole in communication with a formation fluid. To mitigate the associated problems with seal leakage, the multi-stage injector 10 of the present embodiment is housed inside a pressure vessel 70. This pressure vessel 70 provides for pressure compensation within the multi-stage injector 10. In accordance with one embodiment of the present invention, the pressure vessel 70 may be filled with carrier phase at a pressure higher than the highest expected fluid sample pressure. Using a pressure vessel 70 in the recited manner, leakage, if any, would introduce carrier phase into the system, rather than vent it into the environment. Any introduced carrier phase would then exit the multi-stage injector 10 along with a fluid sample through one or more injector outlets 60. This injector outlet may be coupled to another multi-stage injector or may communicate directly with a fluid analysis instrument (not shown). In so far as the leakage is very small, this mode is preferable since it could have negligible effect on the quality of the analysis preformed by the fluid analysis instrument. This “internal leakage” is of primary importance for quantitative analysis, as it guarantees that all mass injected into the system remains within the system.
In accordance with the present embodiment, upon rotation of the rotor 30 around the centerline 50, the fluid within the first cavity 14 at Port A would initially be disconnected from the fluid inlet port 11 of the stator. Following the appropriate rotation of the rotor, this first fluid cavity may be rotated to a position such that the first fluid cavity 14 is now positioned to be in communication with the carrier phase inlet 16. This is the position formerly occupied by the second cavity 18. As the orientation of the first and second cavities 14, 18 are fixed in relation to the rotor 30 and the centerline 50 around which it rotates; the second cavity 18 now occupies the position formerly occupied by the first cavity 14 thereby completing the fluid pathway between the fluid inlet 11 and fluid outlet 12.
For the ease of describing the present embodiment, it will be assumed that the carrier phase supplied at the carrier phase as inlet 16 is at a lower pressure than the pressure of the fluid at the fluid inlet 11. As recited previously, the present invention is not limited to such an arrangement and the prior statement is not intended to be limiting in scope.
Following the aforementioned rotation of the rotor 30 about the centerline 50, the fluid trapped within the first cavity 14 is at a higher pressure than the carrier phase delivered at carrier phase inlet 16. As the carrier phase delivered at the carrier phase inlet 16 is at much lower pressure than the fluid contained within the first cavity 14 that is now introduced into the carrier phase stream the fluid within the fluid sample within the first cavity 14 may expand, thereby reducing the pressure. This substantially simultaneous pressure regulation stage and injection stage in accordance with the present scenario allows for delivery of the fluid sample to a conditioning stage 20 at a pressure that is most compatible with the conditioning stage 20.
The fluid sample is carried to the conditioning stage 20 via the carrier phase that is introduced to the multi-stage injector 10 via the carrier phase inlet 16. In accordance with one embodiment of the present invention, the conditioning stage 20 may be an expansion chamber. Alternative conditioning stages 20 may be utilized in practicing the present invention, including the use of a conditioning stage that is a vaporization stage.
In accordance with the present embodiment, the expansion chamber may include a porous medium disposed within the expansion chamber. As understood by one skilled in the art, the porous medium may be glass wool or a suitable alternative material that provides a high surface area and low thermal mass for the fluid to rapidly evaporate. Additionally, the porous medium disposed within the expansion chamber may be heated to assist in expansion of the fluid.
In accordance with an alternate embodiment of the present invention, the condition stage 20 may be used to aggregate or segregate components prior to the injections of these, or a subset of these, components of a fluid sample into a fluid analysis instrument by an injection stage 30. The aggregation or segregation of components by a conditioning stage is not an exhaustive list of potential conditioning processes which may be practiced by a conditioning stage 20 in accordance with the present invention. The terms aggregation and segregation are used in reference to the spatial separation, or lack of separation, between adjacent components of the sample within the conditioning stage as a result of the dynamics of evaporation, sample transportation, interactions with the inner surfaces, coatings, or packings within of the conditioning stage, or other similar processes as understood by one skilled in the art. Other definitions of the terms aggregation and segregation, such as molecular aggregation in the synthetic chemistry sense, for example, may or may not apply to the usage in this disclosure, as understood by one skilled in the art.
FIGS. 2A-2C will be used to discuss several important aspects related to sample conditioning and component aggregation or segregation. These figures are solely to illustrate the broad concept of aggregation or segregation of components and are not intended to represent experimental data or to be limiting in scope. For the purpose of clarity, it will be assumed that FIGS. 2A-2C illustrate the concentration distribution exiting a conditioning stage of a multistage injector system for the gas-phase portions of a four-component liquid mixture being injected into a gas-phase analytical system, such as a GC, according to this disclosure. The time axis relates to the time since the liquid sample was introduced into the conditioning stage.
In accordance with one aspect of the present invention, the conditioning stage allows for control over various dynamics of sample including but not limited to depressurization and evaporation. As set forth prior, one suitable conditioning stage is an evaporation stage. In many injection systems, the evaporation stage of a liquid injection into a gas-phase analytical system is tied to the operation conditions of the gas-phase analytical system. For example, the flow through a split/splitless injector of a gas chromatograph (GC) is closely related to the flow through the chromatographic column. This makes it difficult to independently tailor the dynamics of the evaporation stage without changing the dynamics of the chromatography. Although the split ratio can be adjusted to change the dynamics of the evaporation process without changing the inlet pressure of the GC column, more advanced options, such as completely stopping the flow during evaporation, are not easily accommodated. With the multi-stage injection system disclosed here, such options are easily accommodated.
Gas-phase sample can be transferred into the gas-phase analytical system by two different means: first, referred to herein as injection method A, by a sampling valve that removes an aliquot from the conditioning stage and places it within a separate flow line that includes the gas-phase analytical system. One skilled in the art will readily recognize that multiple flow lines and/or analytical systems are possible in accordance with the present invention. A second injection method, referred to herein as injection method B, by a switching valve that allows exit flow into at least two flow paths, where at least one of the flow paths would include at least one gas-phase analytical system. For discussion purposes the term actuation time for injection method A will be used to indicate the time at which the aliquot was removed from the sample flow path (i.e. conditioning stage). Similarly, the actuation times relevant for injection method B relate to the window of time within which effluent from the sample line (i.e. conditioning stage) is allowed to flow into the following flow line (i.e. gas-phase analytical system).
In many analyses, all components of a sample are analyzed, and therefore must be representatively introduced into the analytical system. Biases in the resulting measurements will occur if certain components of the sample are lost during sample introduction or if contamination is acquired (i.e. the original concentration ratios are disturbed). In the case of a liquid sample being introduced into a gas-phase analytical system, this requires evaporation of a sample aliquot in such a way that the relative concentration distribution of the sample components is the same when entering the analytical system as it was in the original sample, such that the analysis provided by the analytical system is representative of the original sample. FIG. 2A shows a scenario where the 4 components evaporate simultaneously and are not retained by the surfaces of the conditioning stage; therefore they arrive at the entrance of the sampling stage simultaneously and in the same relative concentration distribution as they were in the liquid state. Such a process shall herein be defined as aggregation of components. If a sampling device according to injection method A is actuated at 25 seconds, a representative sample will be introduced into the gas-phase analytical system. If a sampling device according to injection method B was switched to the flow path of the down-stream analytical device for some period of time that overlaps with the peaks in 3A, a representative sample would be delivered. Experimental results indicate that it has been possible to achieve this scenario for a liquid sample with a wide range of component volatilities. Typically a significantly wide window can be achieved where the injected sample maintains a representative concentration distribution. By adjusting the dimensions of the conditioning stage and/or the flow rate of mobile phase through the conditioning stage, the peak widths in a scenario such as that shown in FIG. 3A can be widened or narrowed to suit the necessities of a given system.
FIG. 2B shows a similar scenario to that of 3A, however, the four components are evaporating at different rates, resulting in overlapping, non-symmetric distributions with non-overlapping maxima and non-equal peak widths. Such a scenario is herein defined as segregation of components in time. Such a scenario is expected for a low temperature conditioning stage and/or low volatility sample components. For this example, Component 1 would have the highest vapor pressure, component 2 would have a lower vapor pressure than component 1, component 3 would have a lower vapor pressure than component 2, and component 4 would have the lowest vapor pressure of the four components. This scenario would pose a problem in terms of injecting a completely representative sample with injection method A. However, using injection method B, as long as the flow was diverted to the gas-phase analytical system for a period that completely overlaps with the plotted peaks (i.e. a time period including the range from  ̃20 seconds to  ̃350 seconds) a representative sample (in terms of relative mass fractions) would be delivered to the gas-phase analytical system. An alternative viewpoint for the scenario in FIG. 3B is that of pre-selection. By intentionally allowing such a scenario to occur, a limited distribution of sample components can be transferred into the gas-phase analytical system. For example, by using injection method A with an actuation time of about 40 seconds (i.e. the maximum of the peak corresponding to component 1), a large fraction of component 1 will be introduced to the gas-phase analytical system, while much smaller fractions of the less-volatile components are introduced into the system. Such an operation is beneficial for targeted analysis of certain components and/or for cases where certain components can harm the gas-phase analytical system. This is also beneficial for hyphentated techniques where multiple analytical devices are used on the same or multiple portions of a sample to improve the knowledge gained about the sample. For a given sample volatility range, a lower conditioning stage temperature will generally exaggerate the trend shown in FIG. 2B, since vapor pressure is inversely exponentially related to temperature.
FIG. 2C shows symmetric evaporation profiles for four components of decreasing volatility (1 is the most volatile, 4 is the least). In this case, the evaporation of each component required the same amount of time (each has the same peak width), however, each component was retained in some way by the inside surfaces or packing materials of the conditioning stage. One way of accomplishing this would be to use a chromatographic column as part or all of the conditioning stage. This method when paired with injection method A would not function well in providing representative samples to a gas-phase analytical system. However, with injection method B, such a task is quite possible. This scheme offers the potential of sample pre-selection as well, similarly to that discussed above.
In practice, one skilled in the art will recognize that in general sample evaporation in scenarios associated with this invention will be some combination of the scenarios depicted in FIGS. 2B and 2C. Experimental results have indicated that the present invention allows for one to achieve a scenario that is effectively close to that depicted in FIG. 2A.
In accordance with an alternative embodiment of the present invention, a second multi-stage injector may be utilized in reducing the expanded volume to a volume more appropriate for feeding into a fluid analysis instrument
This secondary injection is in keeping with the process set forth prior. Additionally, this secondary injection provides a means to re-sample a small fraction of the large volume of the conditioned, or evaporated, liquid from the first stage of sampling. This embodiment of the present invention thereby provides a system, method and apparatus for providing a compatible volume of injection plug.
In accordance with aspects and embodiments of the present invention, a multi-stage injector having multiple pressure regulation stages, multiple conditioning stages, and multiple injections stages is herein recited. In view of the embodiments recited herein, a multi-stage injector for use in fluid analysis is recited wherein this injector may include multiple pressure stages, multiple conditioning stages, multiple injection stages or some combination thereof. Additionally, the present invention of FIG. 1 may be in communication with multiple fluid analysis instruments, or may further communicate with an additional multi-stage injector.
FIG. 3 is an illustration of an alternative embodiment of the present invention. As illustrated in FIG. 3, a dual-stage injection is illustrated in accordance with an alternative embodiment of the present invention. The embodiment of FIG. 3 compares favorably against traditional on/off valves commonly used in those high pressure, high temperature sampling arrangements known to those skilled in the art, as the present embodiment reduce the effects caused by dead volumes such as fractionation and band broadening. Additionally, should the dead volume of common on/off valves be sufficiently addressed, prior art approaches such as these fail to provide fast injections that do not suffer from the inherent problems of split injections.
In accordance with FIG. 3, the dual stage injection arrangement illustrated allows for the entire evaporated fluid sample to be introduced into a secondary injection stage prior to introduction into a fluid analysis instrument (or an additional injection stage). The compact size and orientation of the present embodiment allows for numerous applications of the present invention, including but not limited to applications such as those encountered in the hydrocarbon exploration and productions industry.
FIG. 3 illustrates a dual injection embodiment of the present invention. For the purposes of clarity, the present embodiment is illustrated using two rotary valves. One skilled in the art will readily appreciate that this dual injection may be accomplished using a single device having a similar means of operation yet taking a sufficiently distinct form. For example, some common non-limiting examples additionally suitable for use with the present invention are rotary valves with internal or external sampling cavities or sampling loops, face-sealing and sliding-plate valves with sampling loops or sampling cavities, and networks of tubing and/or microfluidic channels controlled by micro- or meso-scale valves such as solenoid valves. These alternative embodiments are fully considered embodiments of the present invention and the illustrated embodiment is not intended to be limiting in scope. In view of the above, the dual injection embodiment 300 of the present figure includes a first rotary valve 301, a second rotary valve 302 and a conditioning stage 310 in communication with the first and second rotary valves 301,302. First and second rotary valves 301,302 contain a variety of fluid pathways namely Port A (322), Port B (342), Port C (362) and Port D (382). Additionally, the first and second rotary valve 301,302 are capable of rotation about a central axis such that Ports A-D may complete a fluid pathway. Actuation of the first and second rotary valve 301,302 may be accomplished by an external motivational force such as, but not limited to, an electromagnetic driver, or a hydraulic or pneumatic control. In accordance with one embodiment of the present invention, the carrier phase may further be utilized in actuating the first and second rotary valves 301,302. Furthermore, in accordance with aspects of the present invention, a variety of suitable conditioning stages 310 may be disposed between the first and second rotary valve 301,302. Additionally, there may be one or more suitable conditioning stages, arranged in parallel or series, in communication with the first and second rotary valve 301,302. For the purpose of clarity, the conditioning stage of the present embodiment will be considered an expansion stage. Further associated with this expansion stage may be a heater (not shown). An alternative, non-limiting, conditioning stage may be a vaporization stage capable of vaporizing at least a portion of the fluid sample. Additionally, a suitable vaporization stage for practicing aspects of the present invention may vaporize the entire fluid sample, and further may exhaust a portion of the vaporized sample to a waste output.
In accordance with an embodiment, a fluid sample to be analyzed may be introduced into the first rotary valve 301 via fluid sample inlet 320. Additionally, a carrier phase may be introduced to the first rotary valve 301 through carrier phase inlet 340. In the initial position of the first rotary valve 310, the fluid sample may travel from the fluid sample inlet 320, through the fluid pathway of Port A (322) and exit the rotary valve at the fluid sample outlet 330. In a similar manner, the carrier phase pathway of the first rotary valve 301, when in an initial position, is from the carrier phase inlet 340, through Port B (342) and finally to the carrier phase outlet 350. Additionally, the gas outlet 350 is in communication with the evaporator such that carrier phase introduced at the carrier phase inlet 340 passes into the evaporator when the first rotary valve 301 is in the initial position.
Carrier phase from the outlet 350 of the first rotary valve 301 that passes through the expansion chamber is then introduced into a second carrier phase inlet 360 of the second rotary valve 302 when the second rotary valve is in the initial position. Carrier phase is additionally introduced into a carrier phase inlet 380 of the second rotary valve 302 when the second rotary valve 302 is in the initial position. This carrier phase introduced into the second rotary valve 302 through inlet 380 traverses the pathway defined by Port D 382 to exit via outlet 390. In communication with outlet 390 may be a suitable fluid analysis instrument as understood by one skilled in the art. For example, a high performance liquid chromatograph (HPLC), a gas chromatograph (GC), a super-critical fluid chromatograph (SFC), size exclusion chromatograph (SEC) also known as gel permeation chromatograph (GPC), hyphenated methods such as LC-GC, a chemical sensor, or some combination thereof, may be in communication with outlet 390.
As set forth previously, the first and second rotary valve 301,302 may be actuated such that the various fluid pathways defined by Ports A-D (322,342,362,382) may be connected to alternative inlet and outlet ports. For example, Port A, upon actuation of the rotary valve from an initial position to a displaced position may be connected to the carrier phase inlet 340 and gas outlet 350. Following displacement of the first rotary valve 301 from an initial position, the fluid pathway defined by Port A 322 serves to capture a fixed volume of the fluid originally introduced via fluid inlet 320 (i.e. a fluid sample). Following further displacement of the first rotary valve 301 to a displaced position, the liquid sample in the fluid pathway defined as Port A 322 is introduced into a stream of carrier phase originating from carrier phase inlet 340. In accordance with one embodiment, the fluid sample may be at a higher pressure than the carrier phase. In the alternative, the fluid sample may be at a pressure lower than the carrier phase. In the event that the carrier phase is at a lower pressure as compared to the fluid sample, the fluid sample of Port A 322 will be depressurized. While the first rotary valve is in the displaced position, the fluid sample contained in Part A 322 will further be introduced into the expander/heater of the present embodiment. This Expander may further include a porous distributor capable of assisting in evaporation of the fluid sample. The length and volume of the expander/heater may be sized such that the entire sample from the cavity of Port A 322 evaporates before entering the second rotary valve 302, or conversely such that effective pre-selection is achieved such that only the intended components are fully evaporated and transferred to rotary valve 302.
While traversing the expander 310, the volume of the fluid sample increases and the initial substantially liquid sample may be converted into a substantially gaseous sample. The volume of the expanded sample may be too great for introduction into traditional fluid analysis instruments, as set forth previously, therefore the second rotary valve 302 may be utilized in producing a properly sized gas “slug” for introduction into a fluid analysis instrument. The second valve shown here is a preferred embodiment since it introduces a known and small volume of the gas-phase sample into the column reliably, without potential variations in injection volume or excessive use of carrier phase.
Additionally, while the first rotary valve is in the displaced position, the fluid channel defined by Port B 342 completes the fluid pathway from the fluid inlet 320 to the fluid outlet 330. One skilled in the art will further recognize that additional rotary valves, or their equivalent, may be added to the present invention such that at least one appropriate sample is introduced into at least one fluid analysis instrument.
The process of expansion increases the volume of sample, now in the gas phase, to a level too high for introduction directly into a column, as described earlier. The now substantially gaseous fluid sample from the conditioning stage 310 is introduced into inlet 360 of the second rotary valve 302. In accordance with the present invention, this second rotary valve is used as an injection stage. When the second rotary valve 302 is in the initial state, this sample from inlet 360 traverses the fluidic pathway of port C 362 and is exhausted to waste via outlet port 370. Upon actuation of the second rotary valve 302, a similar second sample confined in the fluid channel of port C 362 is connected to the second carrier phase inlet 380. This second fluid sample contained in port C 362 may be of a predefined volume, absent of dead volume effects, and is delivered to a fluid analysis instrument in communication with outlet port 390. As the volume of port C 362 is known, potential variations in injection volume and the excess use of carrier phase are avoided. When the present invention is deployed in an environment such as a borehole, wherein a limited quantity of carrier phase is available, the reduced reliance on carrier phase flow is beneficial in providing multiple samples to a fluid analysis instrument without the need for carrier phase replenishment and in reducing the volume of inert carrier phase that may need to be discharged into the environment as waste.
In the present Figure, a single fluid analysis output 390 is shown into which a gas-phase sample at a regulated pressure may be fed. For example, a gas phase sample at a low pressure may be introduced into a GC column in communication with outlet port 390. In accordance with one embodiment, both valves 301,302 and the heater/expander 310 would be kept at temperatures that would maintain the fluid integrity, thereby preventing the fluid from condensing or fractionating.
Additionally, in accordance with an alternate embodiment of the present invention, applications where the original substantially liquid fluid to be analyzed is at high pressure, the evaporated volume of the sample emerging from the conditioning stage 310 would take a finite but long time to evacuate through the second valve. This enables a convenient timing sequence for the second valve to inject into separate fluid analysis instruments for simultaneous parallel analyses if a multi-port (6, 8, or more) valve is used (not shown). Also possible is the use of multiple sampling loop volumes for injection into a single or multiple columns or fluid analysis instruments. The advantage of this would be that the fluid analysis instrument detector signal-to-noise ratio can be optimized while minimizing overload.
As set forth previously, the conditioning stage 310 of the present invention may be an expansion chamber. The dynamics of the expansion chamber offer several potential advantages in view of the intended application of the present invention. The flow rate and internal volume of the expansion chamber will greatly affect the evaporation profile of various sample components. This can be tuned to allow for complete evaporation of all species, or to selectively avoid components of certain volatility ranges. By sampling the evaporated band with a secondary injector, tailing profiles can be eliminated. Alternatively, this technique can be employed to monitor the evaporation profile of different species by injecting multiple aliquots of a single sample at different times during conditioning of the sample into one or more analytical systems.
Furthermore, inherent in the prior art approaches to sampling, deposition of residual low-volatility components on the inner walls of the injection system and/or down-stream analytical components (e.g. a column) is common. Such a deposition negatively affects the accuracy, precision, and/or other measures of performance of the fluid analysis conducted by the fluid analysis instrument. The present invention, in contrast, offers specific advantages in this regard as the conditioning chamber, which may be an expansion chamber or vaporization chamber for example, can be continually flushed with carrier phase. This additionally can be accomplished at higher temperatures and flow rates than those permitted by modern fluid analysis instruments such as GC columns as it is the secondary injector that provides fluidic and thermal isolation between these two stages. This increased temperature and flow rate allow for faster evaporation of residual components, and the fluidic isolation allows for these evaporated species to be vented rather than injected into the fluid analysis instrument. In view of this, fluid analysis instrument maintenance sequences, such as back flushing or baking of a GC column, can potentially be obviated.
FIG. 4A is an alternative embodiment of the present invention. The present embodiment is shown for illustrative purposes and is not intended to be limiting in scope. One skilled in the art will readily appreciate that numerous alternative elements may be substituted, added, or subtracted from the present embodiment without limiting the current invention.
The present embodiment illustrates the use of a commercially available solenoid valve 40 for use in multi-stage injection. The solenoid valve 40 includes an actuator 41 for use in actuating a commercially available valve. The actuator 41 illustrated is an electromagnetic actuator capable of displacing a plunger 42 from an initial position to a displaced position. One skilled in the art will recognize that the actuator 41 need not be an electromagnetic actuator, and may me actuated by any suitable external force, such as but not limited to a hydraulic, pneumatic or piezoelectric force. The solenoid valve 40 allows for the control of a fluid through a fluidic passageway (not shown). The present embodiment includes modifications beyond commercially available solenoid valves such that multiple flow passages are provided.
FIG. 4B illustrates the fluidic pathways of the present solenoid valve 40 in an un-actuated state. Carrier phase inlet 44 having a first pressure, sample inlet 48 having a second pressure, and outlet 46 are all illustrated. The first pressure of the carrier phase inlet 44 may be higher or lower than the second pressure of the sample inlet 48. Additionally, the outlet 46 may be coupled to an additional pressure regulation stage, conditioning stage, injection stage or to a variety of fluid analysis instruments. Ball 45, is in communication with plunger 42, such that the ball serves as a sealing mechanism and valving mechanism capable of connecting and disconnecting the carrier phase inlet 44 or the sample inlet 48 to the outlet 46 upon actuation. As illustrated in the present embodiment, the ball 45 is disposed such that a fluid pathway from the carrier phase inlet 44 to the outlet 46 is provided, while the sample inlet 48 remains blocked.
FIG. 4C illustrates the actuation of the actuator 40 such that the ball 45, in communication with the plunger 42, is displaced from an initial position to a displaced position. While the ball is in the displaced position, the sample inlet 48 is connected to the outlet 46, while simultaneously the carrier phase inlet 44 to outlet 46 pathway is blocked. The actuator 40 of the present embodiment may be controllably pulsed such that the ball 45 either allows a fluid pathway from sample inlet 48 to outlet 46 or from carrier phase inlet 44 to outlet 48. In accordance with one aspect of the present invention, the pulsing of the plunger 42 and associated ball 45 may be rapid in nature such that the rapid actuation allows for the delivery of a small defined plug of the sample, via the sample inlet 48, to be delivered to the outlet 46. For clarity, it will be assumed that the sample inlet 48 is at a higher pressure than the carrier phase inlet 44. Rapid pulsing of the ball 45 and plunger 42 therefore provides a mechanism wherein the sample is injected into the fluid pathway of carrier phase such that a pressure reduction occurs prior to delivery to the outlet 46. In accordance with aspects of the present embodiment, the solenoid valve 40 may further be pressure compensated.
FIG. 5 is a flowchart illustrating the steps necessary in practicing a method of the present invention. In accordance with the method of the present invention, at least one pressure regulation stage is provided 500, wherein this at least one pressure regulation stage regulates a fluid sample from a first pressure to a second pressure. In accordance with step 502, at least one conditioning stage is provided, wherein the conditioning stage is in communication with the at least one pressure regulation stage and is further configured to receive the fluid sample. Finally, in accordance with step 504, at least one injection stage is provided such that the injection stage is in communication with the conditioning stage and is further configured to provide at least a portion of the fluid sample to a fluid analysis instrument.
The foregoing description is presented for purposes of illustration and description, and is not intended to limit the invention in the form disclosed herein. Consequently, variations and modifications to the inventive parameter measurement systems and methods described commensurate with the above teachings, and the teachings of the relevant art, are deemed within the scope of this invention. These variations will readily suggest themselves to those skilled in the relevant oilfield, fluid analysis, and other relevant industrial art, and are encompassed within the spirit of the invention and the scope of the following claims. Moreover, the embodiments described (e.g. the use of four port rotary valves) are further intended to explain the best mode for practicing the invention, and to enable others skilled in the art to utilize the invention in such, or other, embodiments, and with various modifications required by the particular applications or uses of the invention. It is intended that the appended claims be construed to include all alternative embodiments to the extent that it is permitted in view of the applicable prior art.

## Claims

1. A multi-stage injector for fluid analysis, said multi-stage injector comprising:
at least one pressure regulation stage adapted for receiving a fluid sample, wherein said at least one pressure regulation stage regulates a received fluid sample from a first pressure to a second pressure;
at least one conditioning stage in communication with said at least one pressure regulation stage, said at least one conditioning stage configured to receive said fluid sample from said pressure regulation stage, wherein the at least one conditioning stage comprises an expansion chamber; and
at least one injection stage in communication with said at least one conditioning stage, wherein said at least one injection stage is configured to provide at least a portion of said fluid sample to a fluid sample analysis instrument.

2. The multi-stage injector of claim 1, wherein one of said at least one pressure regulation stage, said at least one conditioning stage and said at least one injection stage is pressure compensated.

3. The multi-stage injector of claim 1, wherein said at least one pressure regulation stage regulates a first high pressure to a second lower pressure.

4. The multi-stage injector of claim 1, wherein said at least one pressure regulation stage regulates a first low pressure to a second high pressure.

5. The multi-stage injector of claim 1, wherein said at least one pressure regulation stage is a multi-port rotary valve.

6. The multi-stage injector of claim 1, wherein said at least one pressure regulation stage is a solenoid valve.

7. The multi-stage injector of claim 1, wherein said at least one expansion chamber provides a volume increase in the fluid sample.

8. The multi-stage injector of claim 1, further comprising a distributor.

9. The multi-stage injector of claim 1, wherein said at least one injection stage is in communication with at least one chromatographic column.

10. The multi-stage injector of claim 1, wherein said at least one injection stage is in communication with a parallel arrangement of chromatographic columns.

11. The multi-stage injector of claim 1, wherein said at least one injection stage is in communication with a chromatographic column or a GC.

12. The multi-stage injector of claim 1, wherein said at least one injection stage is in fluid communication with a second injection stage.

13. The multi-stage injector of claim 1, wherein said multi-stage injector is configured to pressure regulate and condition the fluid sample substantially simultaneously.

14. The multi-stage injector of claim 1, wherein said at least one condition stage aggregates individual components of a fluid sample in time.

15. The multi-stage injector of claim 1, wherein said at least one conditioning stage segregates individual components of a fluid sample in time.

16. The multi-stage injector of claim 1, wherein said at least one injection stage is in communication with at least one of a chromatographic column, a GC, a HPLC, a SFC, a SEC, a GPC, a LC-GC, a MS, an IMS, a DMS, or a chemical sensor.

17. The multi-stage injector of claim 1, wherein at least one of said first and second pressures is at least about 500 psi.

18. The multi-stage injector of claim 1, wherein said at least one injection stage delivers a sharp small plug to an associated fluid analysis device.

19. The injection stage of claim 18, wherein said small sharp plug is delivered to a secondary chromatographic column.

20. The multi-stage injector of claim 1, wherein said at least one pressure regulation stage further comprises a carrier phase pathway for transmission of a carrier phase.

21. The multi-stage injector of claim 20, wherein said carrier phase pathway is at a lower pressure than said first pressure.

22. The multi-stage injector of claim 20, wherein said carrier phase pathway is at a higher pressure than said first pressure.

23. The multi-stage injector of claim 1, wherein said at least one conditioning stage comprises a vaporization stage.

24. The multi-stage injector of claim 23, wherein said vaporization stage vaporizes an entire fluid sample.

25. The multi-stage injector of claim 23, wherein said vaporization stage vaporizes a portion of a fluid sample.

26. The multi-stage injector of claim 23, wherein at least a portion of said fluid sample is exhausted to waste.

27. The multi-stage injector of claim 23, wherein said vaporization stage further comprises a vaporization heater, wherein said vaporization heater is controlled in accordance with a predefined heat ramp.

28. The multi-stage injector of claim 1, wherein said at least one conditioning stage comprises a compression chamber.

29. The multi-stage injector of claim 28, wherein said compression chamber is temperature modulated.

30. The multi-stage injector of claim 28, wherein said compression chamber condenses at least a portion of the sample.

31. A multi-stage fluid injection method, comprising:
providing at least one pressure regulation stage adapted for receiving a fluid sample, wherein said at least one pressure regulation stage regulates a received fluid sample from a first pressure to a second pressure;
providing at least one conditioning stage in communication with said at least one pressure regulation stage, said at least one conditioning stage configured to receive said fluid sample from said pressure regulation stage, wherein the at least one conditioning stage comprises an expansion chamber;
providing at least one injection stage in communication with said at least one conditioning stage; and
injecting at least a portion of the fluid sample to a fluid analysis instrument.

32. The method of claim 31, further comprising the step of pressure compensating at least one of said at least one pressure regulation stage, said at least one conditioning stage and said at least one injection stage is pressure compensated.

33. The method of claim 31, wherein said at least one pressure regulation stage further comprises a carrier phase pathway for transmission of a carrier phase.

34. The method of claim 31, wherein said at least one conditioning stage comprises a compression chamber.

35. The method of claim 31, wherein said at least one injection stage is in communication with a chromatographic column or a GC.

36. The method of claim 31, further comprising the step of providing a second injection stage.

37. The method of claim 31, further comprising the step of providing pressure regulation and conditioning substantially simultaneously.

38. The method of claim 31, further comprising the step of aggregating within the at least one conditioning stage, individual components of a fluid sample in time.

39. The method of claim 31 further comprising the step of segregating within the at least one conditioning stage, individual components of a fluid sample in time.

40. The method of claim 31, wherein said at least one injection stage is in communication with at least one of a chromatographic column, a GC, a HPLC, a SFC, a SEC, a GPC, a LC-GC, a MS, an IMS, a DMS, or a chemical sensor.

41. The method of claim 31, wherein at least one of said first and second pressures is at least about 500 psi.

42. The method of claim 31, wherein said at least one conditioning stage comprises a vaporization stage capable of vaporizing at least a portion of a fluid sample.

43. The method of claim 42, further comprising the step of providing a vaporization heater, wherein said vaporization heater is controlled in accordance with a predefined heat ramp.

44. A multi-stage injector for fluid analysis, said multi-stage injector comprising:
at least one pressure regulation stage adapted for receiving a fluid sample, wherein said at least one pressure regulation stage regulates a received fluid sample from a first pressure to a second pressure;
at least one conditioning stage in communication with said at least one pressure regulation stage, said at least one conditioning stage configured to receive said fluid sample from said pressure regulation stage; and
at least one injection stage in communication with said at least one conditioning stage, wherein said at least one injection stage is configured to provide at least a portion of said fluid sample to a fluid sample analysis instrument;
wherein said multi-stage injector is configured to pressure regulate and condition the fluid sample substantially simultaneously.

45. The multi-stage injector of claim 44, wherein said at least one pressure regulation stage is a multi-port rotary valve.

46. multi-stage injector of claim 44, wherein said at least one conditioning stage comprises an expansion chamber.

47. The multi-stage injector of claim 44, wherein said at least one conditioning stage comprises a vaporization stage.