Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
  • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
  • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
  • G01N21/274—Calibration, base line adjustment, drift correction
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH DRILLING; MINING
  • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B47/00—Survey of boreholes or wells
  • E21B47/10—Locating fluid leaks, intrusions or movements
  • E21B47/113—Locating fluid leaks, intrusions or movements using electrical indications; using light radiations
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH DRILLING; MINING
  • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B47/00—Survey of boreholes or wells
  • E21B47/10—Locating fluid leaks, intrusions or movements
  • E21B47/113—Locating fluid leaks, intrusions or movements using electrical indications; using light radiations
  • E21B47/114—Locating fluid leaks, intrusions or movements using electrical indications; using light radiations using light radiation
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
  • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
  • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
  • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
  • G01N21/64—Fluorescence; Phosphorescence
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/84—Systems specially adapted for particular applications
  • G01N21/85—Investigating moving fluids or granular solids
  • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/26—Oils; viscous liquids; paints; inks
  • G01N33/28—Oils, i.e. hydrocarbon liquids
  • G01N33/2823—Oils, i.e. hydrocarbon liquids raw oil, drilling fluid or polyphasic mixtures
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2201/00—Features of devices classified in G01N21/00
  • G01N2201/08—Optical fibres; light guides
  • G01N2201/084—Fibres for remote transmission

Definitions

• the current invention is directed to the analysis of fluids. More specifically, the current invention is directed to the compositional analysis of fluids, such as fluids produced by oil wells, that contain constituents that fluoresce and/or absorb radiation, such as near-infrared radiation.
• UV-Vis ultraviolet-visible
• IR infrared
• UV fluorescence spectroscopy UV fluorescence spectroscopy
• nuclear magnetic resonance spectroscopy mass spectrometry
• gas chromatography gas chromatography
• Light may scatter as a result of several different mechanisms. If more than one phase is present in the fluid, light will be scattered by reflection and refraction at the interfaces between the phases. Scattering will also occur as a result of the Rayleigh mechanism. Light scattered by the Rayleigh mechanism has the same wavelength as that of the incident light. In some substances, such as oil, scattering also occurs by the Raman phenomenon. Raman scattering produces extremely low intensity light (relative to the intensity of the incident light) having wavelengths both above and below that of the incident light, so that even monochromatic light yields scattered light in a range of wavelengths. Thus, when analyzed by a spectrograph, Raman scattering produces lines on both sides of the Rayleigh line that are a characteristic of the substance and upon which the light is incident can be used its composition.
• the light emitted as a result of Raman scattering is too low in intensity to be transmitted to the surface for analysis, while the down hole environment is too harsh to permit the use of the sensitive equipment, such as a spectrograph and charged couple device, necessary to conduct a Raman analysis down hole.
• a portion of the light entering the fluid may be absorbed.
• the amount of light absorbed at a given wavelength is a characteristic of the substance. Therefore, the constituents of a substance can be determined by comparing the spectrum of the light directed into the fluid with that of the light that has been transmitted through it so as to determine the spectrum of the light absorbed by the fluid. This spectrum may be expressed, for example, as -log, 0 of the ratio of the light directed to the fluid and the light transmitted through the fluid.
• absorption is primarily a function of the constituents of the fluid
• scattering also depends on the physical form of those constituents. For example, in an emulsion, such as a mixture of water and oil, the more finely dispersed the oil droplets the greater the scattering. The increase in scatting associated with the reduction in droplet size will reduce the intensity of the transmitted light, despite the fact that the composition of the fluid, in a quantitative sense, has remained unchanged. Scattering can, therefore, lead to significant errors in systems measuring the absorption spectra of the fluid.
• U.S. patent 4,994,671 discloses a method for analyzing the composition of fluid in a well by suspending within the well a tool that contains a spectrograph and an incandescent tungsten-halogen lamp.
• the lamp is characterized as being relatively bright in the 1000 to 2500 nm range and down to about 500 nm and having acceptable emissions from 350 to 500 nm.
• the lamp directs light onto a sample of fluid that is admitted into the tool. Different sections of a fiber optic bundle receive the light transmitted across the fluid sample, as well as the light back-scattered from the sample.
• the spectra of both the transmitted light and the back scattered light are measured by a spectrograph and the data are digitized and transmitted electronically to a computer at the surface.
• Two absorption spectra for the fluid are determined by dividing the transmitted light spectrum and the back scattered light spectrum by the spectrum of the source light. If the fluid is sufficiently transparent to transmit an adequate amount of light through it, Safinya recommends the use of the transmitted light; otherwise the back- scattered light may be used.
• the computer determines the constituents of the fluid sample by comparing the transmitted or back-scattered absorption spectra to a data base containing reference spectra for water, gas and various types of oils, and using a least squares or principal component analysis method.
• Safinya does not account for the effect of variations arising from scattering.
• the flow of a multicomponent fluid (e.g. , oil, water and gas) through a production well has very complex multiphase properties. Variations will occur not only in terms of the relative proportion of the constituents but also in multiphase characteristics, such as droplet or bubble size and the composition of the continuous and dispersed phases (e.g. , oil and gas bubbles dispersed in water, oil droplets dispersed in gases, etc.). Additionally, there may be paniculate matter suspended in the fluid, which can add to the scattering.
• the intensity of the transmitted light will decrease at all wave lengths, including the intensity of the light in the wave lengths associated with water, which will be interpreted as a greater absorption in the water-associated wave lengths. This, in turn, will lead to the erroneous conclusion that the concentration of water in the fluid has increased.
• a method of determining the concentration of at least one predetermined constituent in a fluid flowing through a downhole portion a well comprising the steps of (i) generating a beam of light, (ii) directing the beam of light into the fluid flowing through the downhole portion of the well so as to cause light to emerge from the fluid, the emerging light having been scattered by the fluid and comprised of components each of which has a different wavelength, (iii) transmitting at least a portion of the emerging light to a location proximate to the surface of the earth, (iv) measuring the intensity of each of at least a portion of the components of the transmitted light, each of the light components in the portion of light components having a wavelength falling within a predetermined range of wavelengths, the light component intensity measurements being conducted at the location proximate the surface,
• the method further comprises the step of determining the weighting factors by (i) directing a calibration beam of light into a plurality of fluid calibration mixtures so as to cause light to emerge from each of the calibration mixtures that is comprised of components each of which has a different wavelength, with each of the calibration mixtures containing predetermined varying concentrations of the constituent, (ii) measuring the intensity of each of the components of the light emerging from the calibration mixtures having a wavelength falling within the predetermined range of wavelengths, (iii) normalizing at least a selected portion of the measured intensities of the light components emerging from the calibration mixtures, and (iv) performing a regression analysis on the normalized intensities of the calibration mixtures so as to determine the weighting factors.
• the invention also encompasses an apparatus for determining the concentration of a predetermined constituent in a fluid flowing through a downhole portion a well, comprising (i) means for generating a beam of light, (ii) means for directing the beam of light into the fluid flowing through the downhole portion of the well so as to cause light to emerge from the fluid which light is comprised of components each of which having a different wavelength and that has been scattered by the fluid prior to emerging therefrom, (iii) means for transmitting at least a portion of the emerging light to a location remote from the downhole portion of the well, (iv) means for measuring the intensity of each of the components of the transmitted light having a wavelength falling within a predetermined range of wavelengths at the remote location, (v) means for exponentially raising and normalizing at least a selected portion of the measured component intensities so as to minimize the effect of the scattering to the light emerging from the fluid has been subjected on the component intensities, (vi) means for determining the concentration of the constituent based upon the normalized component intensities.
• the apparatus further comprises a computer, and the means for means for normalizing the selected portion of the measured component intensities and the means for determining the concentration of the constituents comprises software programmed into the computer.
• Figure 1 is schematic diagram of the fluid analysis system according to the current invention installed in a section of pipe.
• Figure 2 is a transverse cross-section through the sensor shown in Figure
• Figure 2a is a detailed view of the sensor shown in Figure 2.
• Figure 3 is a longitudinal cross-section taken along line III-III shown in Figure 2.
• Figure 3a is a transverse cross-section through the mixer shown in Figure 3, taken along line Illa-IIIa.
• Figure 4 is schematic diagram of an alternate embodiment of the fluid analysis system according to the current invention installed in a section of pipe.
• Figure 5 is schematic diagram of the equipment for performing a calibration according to the current invention.
• Figure 6 is a plot of measured light intensity versus wavelength for oil/ water mixtures ranging from 0 to 100% oil using the near-IR attenuation method.
• the X-axis is the light wavelength in nanometers.
• the Y-axis is the instrument's response in analog to digital converter counts.
• Figure 7 is a plot of normalized light intensity versus wavelength based on the data shown in Figure 6.
• the X-axis is the light wavelength in nanometers.
• the Y- axis is the instrument's response in analog to digital converter counts.
• Figure 8 is a plot of predicted concentration C p versus measured concentration C m for oil using an algorithm according to the current invention based on the data shown in Figure 6.
• Figure 9 is a plot of measured light intensity versus wavelength for oil/water mixtures ranging from 0 to 100% oil using the near-IR fluorescence method.
• the X-axis is the wavelength in Pixel number.
• the Y-axis is the instrument's response in arbitrary units.
• Figure 10 is a plot of normalized light intensity versus wavelength based on the data shown in Figure 9.
• the X-axis is the wavelength in Pixel number.
• the Y- axis is the response in arbitrary units.
• Figure 11 is a plot of predicted concentration C p versus measured concentration C m for oil using an algorithm according to the current invention based on the data shown in Figure 9.
• Figure 12 is a plot of measured light intensity versus wavelength for isooctane/oil/water mixtures ranging from 0-50 % isooctane using the near-IR attenuation method.
• the X-axis is the wavelength in nanometers.
• the Y-axis is the response in arbitrary units.
• Figure 13 is a plot of measured light intensity versus wavelength for isooctane/oil/water mixtures ranging from 0-25 % isooctane using the near-IR attenuation method.
• the X-axis is the wavelength in nanometers.
• the Y-axis is the instrument's response in arbitrary units.
• Figure 14 is a plot of normalized light intensity versus wavelength based on the data shown in Figure 13.
• the X-axis is the wavelength in nanometers.
• the Y- axis is the response in arbitrary units.
• Figure 15 is a schematic diagram showing the software programed into the computer portion of the fluid analyzer shown in Figure 1.
• Figure 16 is a schematic diagram of a multilateral well into which downhole fluid analyzers according to the current invention have been incorporated.
• the concentration of certain constituents in a fluid can be determined by directing light to the fluid, sensing the light emerging from the fluid, measuring the relative intensity of the components of the sensed light at selected wavelengths, and then treating these relative component intensities according to an algorithm, developed for the particular fluid being analyzed, that weights the component intensities using predetermined weighting factors based on the wavelength associated with each component.
• an algorithm developed for the particular fluid being analyzed, that weights the component intensities using predetermined weighting factors based on the wavelength associated with each component.
• the algorithm to be used in calculating the concentration of a particular constituent can be developed by measuring the intensity of the components of the light emerging from various known mixtures of the fluids to be analyzed over a range of wavelengths. These mixtures are formed by varying the concentration of the particular constituents in the fluid in a known way. After normalizing the component intensities, a regression analysis, such as a partial least squares regression, is used to determine the weighting factors that indicate the weight to be attached to the normalized component intensity at each wavelength. Based on these weighting factors, an algorithm is developed for calculating the concentration of the constituent.
• a regression analysis such as a partial least squares regression
• either the phenomenon associated with the attenuation of radiation (e.g. , as a result of absorption) or the excitation of fluorescent radiation may be used to determine the concentration of a particular constituent of the fluid.
• a beam of light is directed to the fluid.
• the emerging light may be attenuated as a result of absorption and/or scattering.
• the light may induce fluorescence.
• the light emerging from the fluid will be attenuated and/or comprises fluorescent radiation. The analysis of the emerging light permits the determination of concentration.
• the concentration of oil for example, can be determined using either method.
• concentrations of water and natural gas, which do not fluoresce can only be directly determined using the attenuation method.
• the light directed to the fluid should encompass a broad range of wavelengths.
• the wavelength of the light directed to the fluid should lie within a narrow range, and preferably the light should be monochromatic.
• the light directed to the fluid is preferably in the near infrared ("near-IR") range - that is, having a wavelength from approximately 800 nm to 3000 nm.
• near-IR near infrared
• analysis of the emerging light is based on measurement of the intensity of its components at various predetermined wavelengths.
• the measured intensities are normalized to minimize the errors resulting from scattering.
• each of the measured component intensities is preferably normalized by dividing it by an intensity characteristic associated with all, or at least most, of the components of the emerging light within a predetermined range of wavelength.
• normalization is preferably accomplished by dividing the measured component intensities by an intensity characteristic of the laser light used to induce the fluorescence.
• the amount of light absorbed at a given wavelength is a characteristic of the substance through which the light is travels. While the light that is absorbed cannot be directly measured, the light emerging from the fluid can be measured. As a result of absorption, the intensity of the emerging light will be reduced or "attenuated. " The amount of attenuation of the light for any given composition will varying as a function of its wavelength. Thus, for a given source light spectrum, evaluating the intensity of the components of the emerging light at selected wavelengths provides information about the composition of the fluid. Scattering also causes attenuation of the light intensity. However, whereas attenuation as a result of absorption causes relative changes in the light intensity as a function of wavelength, i.e.
• the effects of scattering can be effectively eliminated by normalizing the intensity of the collected light components at each wavelength utilized in the algorithm to the intensity over a broad band of wavelengths.
• an analysis of the relative attenuated components of the light emerging from the fluid can be used to accurately determine the concentration of its constituents, despite the simultaneous presence of scattering.
• the light directed to the fluid preferably encompasses a broad band of wavelengths that, most preferably, is sufficiently broad to encompass all, or at least most, of the major absorption peaks associated with the constituents whose concentration is to be determined.
• the major absorption peaks associated with the constituents whose concentration is to be determined For example, oil and natural gas have absorption peaks at 1200 nm and 1400 nm. Water has absorption peaks at 1150 nm and 1450 nm.
• the light should have wavelengths that at least encompass the 300 nm range as associated with these peaks (i.e. , from 1150 nm to 1450 nm).
• the light directed to the fluid preferably has wavelengths in the near-IR range - that is, having a wavelength from approximately 800 nm to 3000 nm. More preferably, the light is in the range of about 900 nm to 2000 nm, more preferably still in the range of about 1100 nm to 1800 nm, and most preferably in the range of about 1100 nm to 1550 nm.
• Fluorescence is a type of luminescence — that is, light emitted by a process other than combustion or incandescence.
• a flourescent substance When illuminated with light of the appropriate wavelength it absorbs energy which, in turn, excites the absorbing species to a higher energy electronic state. When the absorbing species returns to its electronic ground state, a photon of light is emitted.
• the time between absorption and emission is relatively short and the process is called fluorescence. If the excited state from which the absorbing species decays has a different multiplicity from that of the ground state, the time interval is relatively long, and the process is referred to as phosphorescence.
• the light generated by fluorescence is always of longer wavelength than the incident light. Thus, in fluorescence, the absorption of light of one wavelength results in the emission of light of longer wavelengths.
• Certain molecular arrangements within fluorescent substances, called chromophores are the centers of fluorescent activity. Not all chromophores respond to light in the same way.
• compounds with fused aromatic rings or compounds with a greater number of conjugated multiple bonds can fluoresce when subjected to light at longer wavelengths, specifically, in the visible to near-IR range.
• Less complex, low molecular weight compounds, such as the simple hydrocarbons found in natural gas either do not fluoresce or fluoresce only at shorter wavelengths (in the ultra violet range) but not in the near-IR range. Water does not fluoresce.
• Other substances that do not fluoresce when excited by light in the near-IR range are sand and silt. In general, using excitation light having shorter wavelengths will result in fluorescent radiation of greater intensity, making analysis easier.
• the excitation light from the light source is generated at one location, preferably the surface, and transmitted through fiber optic cables over long distances to fluid at a remote location, such as downhole in an oil well.
• Light having short wavelengths, such as ultraviolet radiation is difficult to transmit over such long distances and can result in excessive Raman scattering.
• light in the near-IR range can be readily transmitted over long distances.
• shorter wavelength light may induce fluorescence in too many substances, making analysis of a particular constituent more difficult.
• near-IR excitation light causes oil, but not natural gas or water, to emit relatively intense fluorescent radiation. Consequently, according to the current invention, the concentration of oil is preferably determined using excitation light having a wavelength within or somewhat below the near-IR range.
• laser light having a relatively narrow wavelength band is directed to the fluid.
• the source should emit light having wavelengths from somewhat below the near-IR range to about the mid near-IR range — that is, from about 500 nm to 1700 nm range.
• the excitation light should be in the range of about the 600 nm to 1000 nm, more preferably still in the range of about the 780 nm to 900 nm, such as laser light having a wavelength of about 780 nm, 808 nm, or 852 nm.
• the laser light passes through the fluid, some of the light is absorbed by and re-emitted as fluorescent light at longer wavelengths than the absorbed light. Some of this fluorescent light is collected, along with some of the laser light that was transmitted through the fluid. For fluids that are highly scattering, the collected laser light intensity will be lower than for fluids that are not highly scattering since in the latter case a greater percentage of the laser light will be collected. Consequently, the laser light scattered by the fluid can be used as a means for monitoring its scattering characteristics.
• the collected fluorescence light will be dependent on both the concentration of fluorescent species present in the fluid and the scattering properties of the fluid. As the concentration of fluorescent species increases, the collected fluorescent light will increase. As the scattering characteristics of the fluid increase, the collected fluorescent light will decrease. Thus, the influence of the scattering properties of the fluid can be corrected for by normalizing the collected fluorescent intensity to the collected laser intensity. (In some circumstances, it may also be desirable to normalize the collected laser intensity itself by the laser intensity at the surface, in order to correct for optical power fluctuations in the laser.) In any event, in the fluorescence method of analysis, evaluation of the normalized intensity of the fluorescent light emitted by the fluid can be used to accurately determine the concentration of its constituents, despite the presence of scattering. III. APPARATUS
• FIG. 1 One embodiment of an apparatus according to the current invention is shown in Figure 1 applied to an instrumented section of pipe 10, which in some applications may be incorporated into production piping 7 disposed in a well bore 5, through which the fluid 3 to be analyzed flows.
• the apparatus shown in Figure 1 can be optimized for use with either the attenuation or fluorescence methods of analysis.
• the instrumented pipe section 10 comprises a sensor 12 that has been incorporated into the pipe. Although only one sensor 12 is shown in Figure 1 , it may be desirable to incorporate a number of sensors into the instrumented section 10, for example, by spacing two or more sensors circumferentially around the pipe at the same axial location and/or spacing two or more sensors axially along the pipe. The use of multiple sensors 12 will reduce errors associated with the fact that the fluid flowing through the instrumented sectionlO may not be uniform across its cross-section or along the length of the section.
• a diagram of one sensor 12 suitable for use in the current invention is shown in Figures 2 and 3 and comprises a notch 19 formed in the inner wall of the pipe section 10.
• Optically transparent windows 30 are formed on opposing walls of the notch 19.
• a focusing lens 32, to which fiber optics 14 are coupled, is located behind each window 30.
• the light 26 from the source 16 exits the first fiber optic 14' , passes through the first lens 32, and then the first window 30.
• the light subsequently passes into and interacts with the fluid stream 3.
• the light emerging from the fluid stream passes through the second window 30 and is focused by the second lens 32 so that it is collected by the second fiber optic 14" .
• the mixer 60 may comprise a section of piping 61 incorporated into the production piping 7 and into which helically extending mixing vanes 66 have been installed to swirl the fluid, thereby ensuring adequate mixing of the constituents before they reach the instrumented section 10.
• the diverter 62 may comprise a section of piping 63 incorporated into the production piping 7 and into which a baffle 64 has been installed.
• the baffle 64 is preferably angled toward the notch 19 of the sensor 12, most preferably at an angle with respect to the axis of the piping that is equal to or greater than the angle of the sloping side wall 19 of the notch, so as to deflect at least a portion, preferably a major portion, of the fluid 3 so that it is directed into the notch 19.
• a filter such as a dielectric filter (not shown), may be incorporated at the probe to filter out emission lines around the laser wavelength so as to eliminate the effect of glass Raman scattering.
• Each sensor 12 is optically connected to a light source 16 and a remote fluid analyzer 6 by a fiber optic cable 13 containing a pair of optical fibers 14' and 14".
• the optical fibers which may comprise a bundle of optical fibers, are of the multimode type.
• the first optical fiber 14' is coupled to a light source 16, which is preferably located at a remote location, such as the surface.
• the second optical fiber 14" is coupled to a fluid analyzer 6, which is also preferably located a remote location, such at the surface.
• the fiber optic cable 13 transmits light from the light source 16 to the sensor 12 and transmits light from the sensor to the fluid analyzer 6.
• a broadband light source 16 When used in connection with the attenuation method, a broadband light source 16 should be used, such as a quartz tungsten halogen lamp.
• the light source 16 emits light having wavelengths sufficiently broad to encompass the major absorption peaks of the constituents whose concentration is to be determined, as previously discussed. In the case of mixtures of oil, water and/or natural gas, the wavelength of the light should encompass the ranges previously discussed in section I.
• the light source 16 should be an extremely narrow band source, and preferably be a monochromatic light source, such as a diode laser or a diode-pumped solid state (DPSS) laser. When used in circumstances requiring transmission of light over long distances, the light source 16 emits light having a wavelength in the ranges previously discussed in section II.
• DPSS diode-pumped solid state
• the fluid analyzer 6 comprises a spectrographic detector 18, a computer 20, and an indicator 22.
• the spectrographic detector 18 includes a spectrograph for dispersing the light from the collection fiber into its component wavelengths and a detector for sensing the intensity at each of these wavelengths.
• the detector may comprise an InGaAs diode array to detect the intensity at each of the dispersed wavelengths.
• Such an array typically has a spectral sensitivity from 900 nm to 1700 nm.
• the primary advantage of using an array for detection is its ability to detect the light intensity simultaneously at every detected wavelength. For scanning systems, whether of interferometric or grating type, each wavelength's intensity is detected at a different discrete time. Since downhole scattering is a temporal phenomenon, this would make the measured effect of the scattering appear to be wavelength dependent.
• the simultaneous detection of intensity at all detected wavelengths ensures that the effects of scattering are common to all wavelengths and facilitates the use of a normalization method to correct for scattering.
• a charge coupled device silicon array may be used for the detector.
• a filter or beam splitter can be used to direct the collected laser signal to one detector while the fluorescent signal is directed to a second detector.
• the detectors can be single element detectors that effectively integrate the signal intensities for all of the impinging wavelengths.
• the output of the detector for the laser signal is proportional to the integrated laser intensity and the output of the detector for the fluorescent signal is proportional to the integrated fluorescence signal. Normalization can be performed by taking the ratio of the two detector outputs in either analog or digital form.
• the computer 20 is programmed with software that allows it to read the array of intensities from the spectrographic detector 18.
• the output of the light source 16 is directed into the proximal end of the first fiber optic 14' located at the surface, as shown in Figure 1.
• the fiber optic 14' permits the transmission of the light downhole to the remote sensor 12.
• the sampling portion of the remote sensor 12 is in contact with the downhole fluid stream 3 that is to be analyzed.
• the source light interacts with the fluid 3, as shown in Figure 3, causing the fluid to absorb, scatter, transmit and/or fluoresce light.
• the second fiber optic 14" collects a portion of the light which is emerging from the fluid stream 3 (which may include scattered light from the source, transmitted light, and fluorescent radiation) and transmits this light to the surface, where its intensity is detected as a function of wavelength using the spectrographic detector 18.
• the data from the spectrographic detector 18 is then input into the computer 20.
• the computer 20 is programmed with software containing an algorithm that determines the composition of the fluid 3 — that is, the concentrations of predetermined constituents, for example, the percentages of oil and water — based on the intensity of the light emerging from the fluid at one or more selected discrete wavelength or range of wavelengths, as determined by the spectrographic detector 18.
• the indicator 22 which may be a digital readout device.
• An apparatus for simultaneously employing both the fluorescence and attenuation methods of analysis is shown in Figure 4.
• two separate light sources 16' and 16" and two separate spectrographic detectors 18' and 18" are utilized.
• the first light source 16' is used for the fluorescence portion of the analysis and, as discussed above, preferably generates monochromatic light.
• the second light source 16" is used for the attenuation portion of the analysis and, as discussed above, preferably generates broad band light.
• the first spectrographic detector 18' is used for the fluorescence analysis and, as discussed above, preferably comprises a diode array.
• the second spectrographic detector 18" is used for fluorescence analysis and, as discussed above, preferably comprises a charged couple device.
• Light from the two sources 16' and 16" may be directed by optic fibers 15' and 15" into a common optic fiber 14' by using a beam combining device 40.
• the beam combining device 40 may consist of a dichromatic beam splitter, a fiber optic coupler, a fiber optic multiplexer, or a similar type of device.
• Light from both light sources 16' and 16" is carried downhole by the common fiber optic 14' to a common sensor 12, such as that previously discussed. After interaction of light from both sources 16' and 16" with the fluid stream 3, light from the fluid stream is collected and returned to the surface by a common carrier fiber optic 14".
• a splitter device 42 which may be a filter, a filter set, a beam splitter, a fiber optic splitter, a fiber optic demultiplexer, a grating, or a similar device.
• One signal comprises light in the wavelength range that incorporates the wavelengths of the first, monochromatic light source 16' and the wavelengths of the fluorescence that was generated downhole by the interaction of light from the monochromatic source and the fluid stream 3.
• This signal is directed to the first spectrographic detector 18' by means of fiber optic 17' .
• the second signal comprises the wavelength range that incorporates the wavelengths of the second, broadband source light source 16" .
• This signal is directed to the second spectrographic detector 18" by means of fiber optic 17" .
• the processing of these independent signals is performed by the computer 20 using the software and algorithms of the current invention, as discussed further below — specifically, a first algorithm developed from an attenuation-based calibration would be used to determine concentration based on the attenuation analysis and a second algorithm developed from a fluorescence-based calibration would be used to determine concentration based on the fluorescence analysis. The concentration resulting from the two methods of analysis could then be compared for verification.
• the computer 20 is programed with software, shown schematically in Figure 15, for determining the concentration based on the light components measured by the spectrographic detector 18.
• the computer 20 first directs the light source 16 to transmit a beam of light to the sensor 12, which directs the light emerging from the fluid to the spectrographic detector 18.
• the computer directs the spectrographic detector 18 to determine the intensity of the components of the emerging light at wavelengths within a predetermined range.
• the normalization factor f n is calculated from the measured intensities, for example using the equation indicated.
• step 130 the measured intensities at selected wavelengths, preprogramed into the computer, are normalized using the normalization factor determined in step 120.
• step 140 the normalized intensities are applied to one or more algorithms preprogramed into the computer so as to calculate the concentration of the constituents of interest.
• step 150 the calculated concentration, for example 90% oil, is displayed on the indicator 22.
• the measured intensities of the light emerging from the fluid are normalized to eliminate the effect of scattering on the analysis.
• normalization is preferably performed using a characteristic of the intensity of the light emerging from the fluid over a range of wavelengths.
• the vector length of the emerging light spectrum is used. Mathematically, the vector length is represented as:
• n a number representing the particular mixture being analyzed
• i represents discrete wavelengths or wavelength ranges
• the measured intensity I ⁇ n at any given wavelength is determined by integrating the intensity over at least a small wavelength band about the given wavelength in order to minimize errors due to slight deviations in wavelength detection.
• the measured intensity at a wavelength of 1100 nm, I noo is determined by integrating the intensity over a wavelength band from 1095 nm to 1105 nm.
• the integrated intensity over a relatively large band of wavelengths e.g. , 950 to 1000 nm
• Normalization is performed by dividing the measured intensity I ⁇ n at each wavelength in the n th spectrum by the vector length f ⁇ so that
• normalization is performed by reference to the intensity of the portion of the collected light that represents the scattered laser light, determined by detecting the intensity of the collected light in a small band of wavelengths around the wavelength of the laser.
• the measured intensities can be normalized by dividing the intensity of the fluorescent radiation at each wavelength I, by the intensity of the transmitted laser light IL (e.g. , determined by measuring the intensity of the transmitted light component at the wavelength of the laser light) so that:
• the concentration of each constituent of interest is preferably determined from an equation of the type:
• kn The concentration of constituent k for mixture n (for example,
• m The total number of light components whose intensities are used in the algorithm, which may, but need not be, the same as the number of light component intensities used in calculating the vector length or other normalization factor.
• the weighting factor for constituent k at each of the selected wavelengths or wavelength ranges i discussed further below.
• CC , Exponents for constituent k at each of the selected wavelengths or wavelength ranges i.
• the weighting factor ⁇ kl for each constituent shows the relative weight to be given the intensity at each of the selected wavelengths in determining the concentration of that constituent — that is, the extent to which the intensity of the light component at a given wavelength is a predictor of the concentration of the constituent of interest.
• the weighting factors may be positive or negative. If all of the wavelengths are used, rather than only the most significant, then some of the weighting factors may be zero.
• the normalized intensity of the light component at each wavelength to be used in the algorithm is multiplied by a weighting factor the value of which is dependent upon the wavelength.
• the normalized and weighted intensities are then summed to arrive at the concentration of the constituent for which the algorithm was developed.
• the wavelengths used for the three equations above were drawn from the same five wavelength set.
• the selected wavelengths for each constituent might come from completely different sets of wavelengths.
• all of the wavelengths used in each of the algorithms would fall within the same range of wavelengths.
• the wavelengths used in the algorithm would all fall somewhere within the near-IR range (e.g. , in the range from 800 nm to 1600 nm).
• the intensity of the light components at the prescribed wavelengths of the light emerging from the fluid flowing in the well is measured using either an attenuation or fluorescence technique.
• These measured component intensities are then normalized, as discussed above. For example, if vector length normalization were used, the vector length of the spectrum over a range of wavelengths (for example, all of the wavelengths in the 1100 to 1500 nm range) would be calculated from the measured intensities and the measured intensity at each of the wavelengths used in the algorithm would then be divided by the vector length so as to arrive at normalized intensities for those wavelengths.
• a set of normalized intensities might be:
• the algorithm might involve two or more equations for each constituent, each covering a different concentration range - for example, one equation for oil concentrations between 0% and 50% and another equation, with different weighting factors and/or selected wavelengths, for oil concentrations between 50% and 100% , etc.
• a Soft Independent Modeling by Class Analogy could be used. In this method, a classification model is generated based on the light intensities of mixtures that fall into the different concentration ranges selected. The model is then used to predict into which concentration range an unknown mixture falls.
• a calibration algorithm optimized for that range can be used to more accurately determine the concentration of the constituents of interest.
• classification models other than SIMCA can be used to achieve the same goal, such as K-nearest neighbors, discriminate analysis, principal component analysis, and neural nets.
• the computer 20 may also be programmed with software for performing the calculations associated with the development of the specific algorithm from the calibration data - that is, the identification of the weighting factors used to weight the importance of the intensities at various wavelengths in determining concentration, as discussed further below.
• Equation 5 The specific form of the algorithm discussed above and shown as equation 5 is developed for each constituent by identifying a range of wavelengths that encompasses those wavelengths whose intensities are likely to provide the maximum information about the concentration of that constituent, determining the weighting factors ⁇ lk associated with each of the wavelengths in the range, and selecting those wavelengths to be used in the algorithm based on the weighting factors . This is done by performing a calibration for the particular type of fluid to be analyzed — for example, the fluid from the well into which the sensor 12 will be installed — and the particular constituents for which concentration is to be determined — for example, the particular type of crude oil being produced by the well.
• Calibration is performed by obtaining quantities of each constituent and preparing various mixtures of differing concentrations that preferably span the range of concentrations to be encountered in operation. For example, if a mixture of crude oil and water from a producing well is to be analyzed, a quantity of pure crude oil extracted from the fluid produced by the well is obtained.
• the sensor 12 is then installed onto a container 50, as shown in Figure 5.
• a stirring device such as a stir plate 52, is used to mix the oil and water in the container 50.
• the sensor 12' which may be similar to the sensor 12 shown in Figures 2 and 3, is coupled to the fluid analyzer 6 and light source 16 using a fiber optic cable 13.
• the light source 16 and fluid analyzer 6 are as discussed above in connection with Figure 1.
• the same type and length of fiber optic cable 13 that will be used in actual service is employed so as to remove the effects of attenuation of the light as it travels through the long fiber optic cable on the calibration results.
• the equipment set up used is shown in Figure 5.
• the container 50 was filled with pure crude oil.
• the crude oil would be extracted from the fluid produced by the well.
• light Pennsylvania crude oil was used.
• the light source 16 used for this experiment was a quartz tungsten halogen lamp, which generated light having wavelengths that encompass the 1100 nm to 1550 nm range.
• the intensity of the source was set just below saturation of the detector at 0.1 sec integration (-50,000 counts/sec). This light was directed by the fiber optic 14' to the sensor 12, which then directed it to the oil in the container 50.
• the light emerging from the oil was collected by the sensor 12 and transmitted by fiber optic 14" to the fluid analyzer 6.
• the fiber optics 14' and 14" were each approximately nine feet long.
• the fluid analyzer 6 employed a diode array to measure the intensity of the emerging light versus its wavelength so as to essentially develop the spectrum of light emerging from pure oil of the type produced by the well. This data was then stored in the computer 20. Since crude oil has absorption peaks at about 1200 nm and 1400 nm, it was determined that the range of wavelengths to be used in the calibration was 1100 nm to 1520 nm. The spectrum of light emerging from pure crude oil in this wavelength range is shown in Figure 6. Since the intensity of the light emerging from the fluid is reduced at those wavelengths at which appreciable absorption occurs, the areas of greatest absorption appear as troughs in the spectrum of the emerging light.
• the spectra shown in Figure 6 and utilized according to the current invention are not the spectra of the absorbed light but rather the spectra of the emerging light from the fluid, which contains those portions of the light that are scattered by or transmitted through the fluid (i.e. , not absorbed).
• the stir plate 52 was used to maintain good mixing of the oil and water.
• the degree of mixing during data acquisition should approximate that of the fluid to be encountered in actual service — for example, the degree of mixing associated with the fluid flowing down hole in the well.
• a spectrum for the 1100 nm to 1550 nm range was obtained by measuring the intensity of the light component at each wavelength within the range so that intensity was measured at a total of 450 wavelengths.
• the intensity of the light from the fluid was measured simultaneously at all wavelength over a 0.1 second period. This measurement was repeated one hundred times and the readings averaged to arrive at a final intensity value for each wavelength. Data acquisition was repeated ten times so that ten sets of data was obtained for each mixture.
• the absolute intensity of the spectra vary quite dramatically with concentration. Specifically, higher concentrations of oil yield low absolute spectral intensities at the wavelengths for which absorption is high. As previously discussed, this results from two phenomena associated with the presence of oil — increased scattering and increased near-IR absorption. However, as also previously discussed, whereas the amount of absorption is a function of only the concentration of oil, the amount of scattering depends upon both the concentration and various multiphase characteristics, such as droplet size. Therefore, according to an important aspect of the current invention, the effect of scattering is minimized by normalizing the spectra. Thus, using the method previously discussed, the vector length of each of the spectra in Figure 6 was calculated. Each spectrum was then divided by its own vector length so as to generate the normalized spectra shown in Figure 7. As can be seen, the peak intensity trends follow concentration, indicating that the normalized spectra are independent of the scattering properties of the various mixtures.
• the resulting raw spectra ranges are shown in Figure 9.
• the scattered laser light is clearly visible at a pixel number slightly greater than 18.
• the measured intensity at each wavelength was then normalized by dividing it by the peak amplitude of the scattered laser light so as to obtain the normalized spectra shown in Figure 10.
• the attenuation method of the current invention can also be used to determine the concentration of natural gas in a fluid flow.
• Natural gas consists mainly of methane (CH 4 ), ethane (C 2 H 6 ) and other small chain hydrocarbons (e.g.
• Figure 11 (1951) used the ratio of these two absorption bands to determine the number of methyl and methylene groups per molecule in paraffins and lubrication oils.
• Figure 11 shows near-IR spectra of crude oil with varying amounts of isooctane (0-50%). As the isooctane concentration increases, the methyl spectral band grows in intensity relative to the methylene band, which allows the method described above to distinguish between the two organic fluids.
• a mixture composed of 67% oil and 33% water was prepared as a starting point. Using the set up shown in Figure 5, the mixture was analyzed using the near-IR attenuation method.
• any one of a number of well know regression techniques can be used to determine the weighting factors ⁇ to be used in weighing the values of the normalized component intensities measured in actual service in order to calculate concentration.
• the preferred regression technique is partial least squares regression.
• two or more techniques may be employed - for example, an initial regression model may be determined based on a partial least squares regression technique and then refined using a multiple least squares regression technique.
• Univariate regression is by far the most familiar technique for correlating spectral data to concentration. In chemical analysis this amounts to correlating the value of the peak spectral intensity IN n of spectrum n with the concentration C n of the constituent k of interest associated with that spectrum.
• the sequence of observations of IN n and C n from mixtures at each of the concentrations to be used in the calibration are used to derive a linear equation:
• ⁇ are essentially weighting factors that relate how much information each measured intensity, at each individual wavelength, contains concerning the concentration C.
• the largest values of the weighting factors ⁇ are associated with the wavelengths that have the most influence on the determination of concentration.
• MLS regression is an adequate procedure in some situations. However, it requires independence of the elements in the matrix subject to inversion — an unlikely situation for collinear spectroscopic data. Also, significant amounts of irrelevant information are likely to be incorporated into the model since every variable is included in the model.
• PCR principal component regression
• the magnitude of a particular loading for a given principle component indicates how much information that wavelength contributes to the principle component. Inspection of the loading matrix may reveal which wavelengths contain the most information about the concentration of the constituent of interest.
• the scores matrix simply relates the principal components back to the original spectra, i.e., the scores define how much a particular principal component contributes to a spectrum. Thus the first row vector of the scores matrix tells how much PC,, PC 2 , etc. , contribute to the particular spectrum.
• the principal components are ranked in order of variance, i.e. PC, accounts for the greatest amount of variance in the set of input spectra. For this reason, the vast majority of the spectral information is included in the first few principal components, while the higher principal components are comprised mostly of noise.
• PCR suffers from a disadvantage in that the correlation between the property of interest and the spectral intensities is not included in the generation of the principle components.
• Partial least squares (PLS) regression also known as Projection to Latent Structures, is described, for example, in Wold, “Partial Least Squares,” in Encyclopedia of Statistic Sciences, Vol. 6, Katz and Johnson, Ed. (Wileyl985), pp. 581-591 and Manne, "Analysis of Two Partial-Least-Squares Algorithms for Multivariant Calibration, " Chemom. Intell. Lab. Syst. (1987) 2: 187-197, each of which is hereby incorporated by reference.
• PLS regression is a procedure that simultaneously estimates the eigenvectors in both the spectral data and the sample property data.
• PLS regression is fundamentally similar to PCR, it has the additional advantage of ordering its factors by considering both the variance of the spectral data and its correlation to the property of interest. Generally, this results in an equivalent or slightly more reliable model than PCR generates.
• An additional advantage of PLS regression involves a much faster computation time (when using a bidiagonalization procedure) compared to PCR.
• PLS regression shares many PCR characteristics — for example, PLS regression finds factors analogous to PCR's principal components. However, because these factors contain information about the correlations, they often yield more parsimonious and, in some situations, more reliable models than PCR.
• regression is preferred, other regression techniques could also be utilized, such as classical least squares, or inverse least squares in addition to any of the other techniques discussed above.
• neural net regression techniques could also be used, especially if the regression model were nonlinear.
• a number of regression techniques suitable for use in practicing the current invention are described more fully in R. Kramer, "Chemometric Techniques For Quantitative Analysis," ISB 0- 824-0198-4, Marcel Dekker (1998), incorporated by reference herein.
• a separate regression is performed for each constituent so that a weighting factors ⁇ , is obtained for each of the selected wavelengths to be used in the algorithm for each constituent.
• component intensities are preferably measured at each wavelength within a preselected range of wavelengths — for example, in the experiments discussed above, algorithms were constructed using the normalized intensity for each wavelength within the 1100 to 1520 nm range for oil using the near-IR absorption method, within the 18 to 770 pixels range for oil using the fluorescence method, and within the 1100 to 1300 nm range for gas using the near-IR absorption method.
• the weighting factor associated with many of these wavelengths (/. e. , those whose intensities can not be readily relied upon to determine concentration of the constituent of interest), however, will be very close to zero. Therefore, if desired in order to simply the computations, the algorithm can be constructed by selecting only key wavelengths within the range - specifically, those wavelengths whose intensities contain the maximum amount of information concerning the concentration of the constituents of interest.
• the wavelengths to be used in the algorithm are determined using a "leave one out" validation technique.
• This algorithm is then used to predict the concentration for the mixture excluded from the calibration and the resulting error determined.
• the calibration calculations are then re-run but this time including the mixture previously excluded but leaving out a different mixture so as to develop another single-wavelength algorithm. Again the error associated with the predicted concentration for the new excluded mixture is determined. This process is repeated until each of the mixtures in the calibration have been left out.
• the predicted residual error sum of the squares (PRESS) associated with this one wavelength algorithm is then calculated.
• the calculations above are then repeated using an algorithm containing the wavelengths having the two highest weighting factors, and the PRESS associated with these algorithms is calculated.
• the calculations are then repeated adding one additional wavelength to the algorithm each time until an algorithm containing all of the wavelengths has been constructed.
• the algorithm that results in the lowest value for PRESS contains the optimum number of wavelengths.
• Calibration results can be improved if the algorithms are limited to certain concentration ranges. This can be accomplished by performing separate regression analyses for mixtures in concentrations within predetermined ranges - for example, mixtures ranging between 0% to 50% oil are used in one regression to arrive at one algorithm and mixtures ranging between 50% to 100% oil are used in another regression to arrive at another algorithm — rather than using all of the mixtures from 0% to 100% in a single regression.
• the near-IR calibration data shown in Figures 6 and 7 were re-analyzed using the same partial least squares regression technique but, this time, the analysis was performed separately for the 0 % to 50% oil concentration range and the 50% to 100% oil concentration range so as to develop two different algorithms, one for each range.
• classification models can be constructed using mixtures compositions of varying pressure and temperature so that the light component data from the flowing fluid can be assigned to a concentration algorithm that has been optimized for the pressures and temperatures having ranges that encompass those of the flowing fluid.
• a multilateral well 4 has three zones extending into the formation 2.
• a section of a production string 8 is located in each zone so that all three zones produce fluids simultaneously.
• Each section of the production string 8 includes a valve 70 for regulating the flow of fluid from its zone.
• the fluid 25 flowing from the well 4 typically may comprise one or more of oil, water, natural gas, and solids, such as sand.
• the fluid 25' , 25" and 25' " from all three zones are combined into a common flow line 25 before reaching the surface.
• an analysis of the fluid at the surface according to a conventional approach will not enable the operator to assess the production of the individual zones of the well.
• a system for analyzing fluid according to the current invention is shown incorporated into each zone of the well 4.
• an instrumented section 10 of the type shown in Figure 1 have been incorporated into the branches of the production piping that extend into each zone of the well, along with a mixer 60 and diverter 62.
• fiber optic cables 14 which may be several kilometers long, connect each of the instrumented sections 10 to the light source 16 and fluid analyzer 6 at the surface.
• the computer 20 of the fluid analyzer 6 is programed with an appropriate algorithm for calculating the concentrations of oil and water, each of which is preferably in the form of equation [5] so that it employs weighting factors for selected wavelengths, which are preferably determined based on a calibration of the oil from the well.
• the light source 16 periodically or continuously transmits light to each of the sensors 12 in the instrumented sections 10 via the optical fibers 14' .
• the intensity of the components of the collected light returned from each of the sensors 12 by the optical fibers 14" over a predetermined range of wavelengths is measured using the spectrographic detector 18.
• the computer 20 periodically or continuously calculates the concentrations of oil and water flowing through each of the zones of the well, using software that allows it to calculate the normalized intensity of the measured light components, preferably using one of the normalization techniques previously discussed, and then apply those normalized intensities to the aforementioned algorithms.
• the calculated concentrations of oil and water are then displayed by the indicator 24.
• Incorporating instrumented sections 10 in each zone of the well 4 allows the operator to determine the percentage of oil and/or water in the fluid flowing downhole through each zone on a nearly real-time basis. This information can, in turn, be used to regulate the flow from each zone so as to optimize production, for example, by operating the valve 70 to reduce the flow from a zone producing a low percentage of crude oil, or excessive water.
• the present invention has been discussed in connection with the determination of the concentration of crude oil or gas in an oil well producing an oil/ ater/gas mixture, the invention can be used to determine the concentration, or merely detect the presence, of oil or gas in other applications, such as when contamination of water by oil is suspected. Alternatively, the invention can be used to determine the concentration or detect the presence of other substances that fluoresce or absorb radiation in flowing streams that have scattering characteristics. Moreover, although the mixer and diverter have been discussed in connection with the sensor of a fluid analyzer, these components could also be used in connection with other types of sensors used in the well piping.

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