US20120074934A1 - Nmr measurements and methods of analyzing nmr data - Google Patents

Nmr measurements and methods of analyzing nmr data Download PDF

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US20120074934A1
US20120074934A1 US12/893,510 US89351010A US2012074934A1 US 20120074934 A1 US20120074934 A1 US 20120074934A1 US 89351010 A US89351010 A US 89351010A US 2012074934 A1 US2012074934 A1 US 2012074934A1
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nmr
data
parameter
measurement
relaxation
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Derrick Green
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Green Imaging Technologies Inc
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Priority to EP11182957.8A priority patent/EP2437078B1/en
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Priority to US14/226,189 priority patent/US9874619B2/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00Arrangements or instruments for measuring magnetic variables
    • G01R33/20Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G01N24/081Making measurements of geologic samples, e.g. measurements of moisture, pH, porosity, permeability, tortuosity or viscosity
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00Arrangements or instruments for measuring magnetic variables
    • G01R33/20Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/448Relaxometry, i.e. quantification of relaxation times or spin density
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00Arrangements or instruments for measuring magnetic variables
    • G01R33/20Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/48NMR imaging systems
    • G01R33/54Signal processing systems, e.g. using pulse sequences ; Generation or control of pulse sequences; Operator console
    • G01R33/56Image enhancement or correction, e.g. subtraction or averaging techniques, e.g. improvement of signal-to-noise ratio and resolution
    • G01R33/563Image enhancement or correction, e.g. subtraction or averaging techniques, e.g. improvement of signal-to-noise ratio and resolution of moving material, e.g. flow contrast angiography
    • G01R33/56341Diffusion imaging
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01VGEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
    • G01V3/00Electric or magnetic prospecting or detecting; Measuring magnetic field characteristics of the earth, e.g. declination, deviation
    • G01V3/18Electric or magnetic prospecting or detecting; Measuring magnetic field characteristics of the earth, e.g. declination, deviation specially adapted for well-logging
    • G01V3/32Electric or magnetic prospecting or detecting; Measuring magnetic field characteristics of the earth, e.g. declination, deviation specially adapted for well-logging operating with electron or nuclear magnetic resonance
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00Arrangements or instruments for measuring magnetic variables
    • G01R33/20Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/46NMR spectroscopy
    • G01R33/4625Processing of acquired signals, e.g. elimination of phase errors, baseline fitting, chemometric analysis

Definitions

  • the present invention relates to nuclear magnetic resonance (“NMR”) measurements and their analysis.
  • NMR is a common laboratory and field tool used throughout many industries.
  • One example is the oil industry which uses NMR to analyze the content and environment of water, oil, and gas in porous media like subterranean reservoir rock.
  • NMR detects the amount of hydrogen (for proton NMR) in a sample or object under study.
  • the lifetime of the detected NMR signal depends on the environment of the hydrogen. For example, an NMR signal detected from hydrogen in oil generally decays faster than an NMR signal detected from hydrogen in free water. In oil field application, differences in the rate of decay of NMR signals can be used to distinguish among for example, oil, water and gas in rock.
  • NMR signal decay times can also be used to distinguish among clay bound (“CBW”), capillary bound (“BVI”) and free fluid (“FFI”) quantities in reservoir rock.
  • T 1 and T 2 are known by those skilled in the art to follow the following equations:
  • is the relaxometry constant
  • D o is the free diffusion constant for the fluid
  • is the gyro magnetic ratio
  • G is the internal field gradient
  • TE is the echo time (a measurement parameter)
  • S/V is the surface to volume ratio of the pores.
  • Equations (1) and (2) above reduce to direct relationships to the surface to volume ratio due to the fact that, in rocks, the bulk relaxation times are much longer than the measured values and typically, an echo time (TE) is selected such that the diffusion term can be ignored.
  • TE echo time
  • the surface to volume ratio is a measure of the pore size distribution of the rock being studied.
  • the relaxation parameters T 1 and T 2 can be measured using many different NMR measurement pulse sequences known to those skilled in the art.
  • a prior art CPMG sequence can be used (see FIG. 1 ) and for T 1 analysis, a prior art inversion recovery sequence can be used (see FIG. 2 ), where RF is the radio frequency excitation pulses, Tau is a delay time equal to 1 ⁇ 2 the echo time (TE) and ACQ is acquired NMR signal.
  • a problem with the above method is that if there is more than one fluid in the porous media being analysed (e.g. subterranean reservoir rock), the results no longer follow the simple equations 1) and 2) above. This makes the results difficult, if not impossible, to interpret.
  • the porous media being analysed e.g. subterranean reservoir rock
  • a method for providing information about a system under study by performing two or more NMR measurements, varying a NMR measurement parameter between these measurements, analyzing each of the measurements separately, then reordering and analyzing the data at each variation used across the measurements.
  • a method for extracting information about a system comprising performing a NMR measurement; acquiring NMR data from the measurement (the data can be a decaying signal dependent on the relaxation parameter T 2 ); expressing the NMR data using a kernel of one dimension; and analyzing the data to extract information (the information extracted can be the NMR relaxation parameter T 2 ).
  • the analysed data can be presented (such on a computer screen display) in the form of a two dimensional map or image.
  • steps can be repeated a sufficient number of times to acquire a sufficient amount of data in three or more dimensions, systematically changing one variable (the variable can be the NMR relaxation parameter T 1 or the molecular diffusion coefficient) to modify the NMR data with each repeat.
  • the acquired data can then be reordered to form a one dimensional kernel across the systematically changed variable.
  • the data can then be analyzed to extract information (the information extracted can be then be dependant on both T 2 and T 1 (or Diffusion)).
  • the acquired NMR data can be compressed and the compressed NMR data can be analyzed using a Butler-Read-Dawson optimization method.
  • a method for performing a NMR measurement on a porous media wherein at least one NMR measurement parameter is used; obtaining a decay signal from the media based on the NMR measurement parameter; altering one of the at least one NMR measurement parameter and repeating these steps.
  • the decay signal can be dependent on the relaxation parameter T 2 .
  • the at least one NMR measurement parameter can be selected from the group consisting of a NMR relaxation parameter T 2 , a NMR relaxation parameter T 1 and a molecular diffusion coefficient.
  • Data can be obtained from the decay signal. The data obtained can depend on one or more of the NMR parameters from the group consisting of the NMR relaxation parameter T 1 , NMR relaxation parameter T 2 and the molecular diffusion coefficient. Steps in the method can be repeated to 3 more dimensions.
  • FIG. 1 is a representative diagram of a prior art CPMG sequence for T 2 analysis
  • FIG. 2 is a representative diagram of a prior art inversion recovery sequence for T 1 analysis
  • FIG. 3 is a diagram of a prior art inversion recovery CPMG sequence
  • FIG. 4 is a diagram of a two dimensional map of a final result of the method according to the present invention.
  • FIG. 5 is a flow diagram of steps according to one or more embodiments of the present invention.
  • FIG. 6 is a schematic diagram of 1D processing steps according to one or more embodiments of the method of the present invention.
  • a NMR measurement inversion recovery CPMG sequence can be used to acquire a plurality of NMR measurements and to systematically vary an NMR measurement parameter, in this case the delay time, T 1 .
  • the number of NMR measurements made will vary depending upon the requirement to have enough data and the duration of the measurement period.
  • Suitable conventional NMR signal acquisition equipment can be used to make the NMR measurements. It will be understood by those skilled in the art that other prior art pulse sequences can also be used for the same purpose.
  • Equation (3) can be solved by minimizing the following equation:
  • A(i) is the amplitude of each exponential decay component
  • T 2 (i) is time
  • t is time
  • TE is the CPMG echo time
  • N is the number of exponential decay components
  • is a smoothing coefficient used in the fitting.
  • Kernel ⁇ ( t , T ⁇ ⁇ 2 ⁇ ( i ) ) ⁇ - t T 2 ⁇ ( i ) ( 5 )
  • the advantage of using a kernel is that it simplifies computation in a computer algorithm. It will be understood by those skilled in the art that computational aspects of the present invention can be computer implemented and performed using a general purpose computer programmed for the purpose.
  • the method of one or more embodiments of the present invention can be stored on non-transitory computer readable memory (such as but not limited to CDs, hard drives, and memory sticks) as statement and instructions for execution by a computer to carry out the method.
  • the data is reordered into a series of one dimensional (“1D”) datasets
  • the first point in each analyzed data set forms the first reordered dataset.
  • These reordered datasets are analyzed one by one using the known equation representing the pulse sequence that created by the variation in NMR measurement parameter. In the case of the pulse sequence shown in FIG. 2 this equation is:
  • the resultant data obtained by solving equation (S) forms a two dimensional (“2D”) result which can be analyzed to look for differences in the parameters in Equation (1) at different values from Equation (2). See FIG. 4 for an example of the result.
  • the resultant value is converted into an image intensity and plotted at an x-y coordinate equal to the parameter from equation (1) and the parameter from Equation (2).
  • the two contour lines 2 and 4 in the image represent different image intensities. While in this example, the T 2 parameter is used for the 1st dimension and T 1 for the second dimension, this can be reversed.
  • the flow diagram of FIG. 5 shows steps of one more embodiments of a method according to the present invention.

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Abstract

NMR measurements and methods of analyzing those measurements are disclosed. A single NMR measurement is performed then that data is analyzed. Additional NMR measurements are performed and analyzed sequentially then the array of NMR analyzed data is analyzed again to get information about the system under study.

Description

    FIELD
  • The present invention relates to nuclear magnetic resonance (“NMR”) measurements and their analysis.
  • BACKGROUND
  • NMR is a common laboratory and field tool used throughout many industries. One example is the oil industry which uses NMR to analyze the content and environment of water, oil, and gas in porous media like subterranean reservoir rock.
  • In general, NMR detects the amount of hydrogen (for proton NMR) in a sample or object under study. The lifetime of the detected NMR signal depends on the environment of the hydrogen. For example, an NMR signal detected from hydrogen in oil generally decays faster than an NMR signal detected from hydrogen in free water. In oil field application, differences in the rate of decay of NMR signals can be used to distinguish among for example, oil, water and gas in rock.
  • NMR signal decay times can also be used to distinguish among clay bound (“CBW”), capillary bound (“BVI”) and free fluid (“FFI”) quantities in reservoir rock.
  • A common method to determine CBW, BV1 and FFI quantities is to use either T2 or T1 relaxation times. The NMR relaxation parameters T1 and T2 are known by those skilled in the art to follow the following equations:
  • 1 T 2 = 1 T 2 - Bulk + ρ S V + ( γ GT E ) 2 D o 12 ( 1 ) 1 T 1 = 1 T 1 - Bulk + ρ S V ( 2 )
  • where ρ is the relaxometry constant, Do is the free diffusion constant for the fluid, γ is the gyro magnetic ratio, G is the internal field gradient, TE is the echo time (a measurement parameter), and S/V is the surface to volume ratio of the pores.
  • Equations (1) and (2) above reduce to direct relationships to the surface to volume ratio due to the fact that, in rocks, the bulk relaxation times are much longer than the measured values and typically, an echo time (TE) is selected such that the diffusion term can be ignored. The surface to volume ratio is a measure of the pore size distribution of the rock being studied.
  • The relaxation parameters T1 and T2 can be measured using many different NMR measurement pulse sequences known to those skilled in the art. For example, for T2 analysis, a prior art CPMG sequence can be used (see FIG. 1) and for T1 analysis, a prior art inversion recovery sequence can be used (see FIG. 2), where RF is the radio frequency excitation pulses, Tau is a delay time equal to ½ the echo time (TE) and ACQ is acquired NMR signal.
  • A problem with the above method is that if there is more than one fluid in the porous media being analysed (e.g. subterranean reservoir rock), the results no longer follow the simple equations 1) and 2) above. This makes the results difficult, if not impossible, to interpret.
  • SUMMARY
  • According to one or more aspects of the disclosed subject matter, a method is described for providing information about a system under study by performing two or more NMR measurements, varying a NMR measurement parameter between these measurements, analyzing each of the measurements separately, then reordering and analyzing the data at each variation used across the measurements.
  • According to one or more aspects of the disclosed subject matter, a method is described for extracting information about a system (the system can be a porous media such as rock) comprising performing a NMR measurement; acquiring NMR data from the measurement (the data can be a decaying signal dependent on the relaxation parameter T2); expressing the NMR data using a kernel of one dimension; and analyzing the data to extract information (the information extracted can be the NMR relaxation parameter T2). The analysed data can be presented (such on a computer screen display) in the form of a two dimensional map or image.
  • These steps can be repeated a sufficient number of times to acquire a sufficient amount of data in three or more dimensions, systematically changing one variable (the variable can be the NMR relaxation parameter T1 or the molecular diffusion coefficient) to modify the NMR data with each repeat. The acquired data can then be reordered to form a one dimensional kernel across the systematically changed variable. The data can then be analyzed to extract information (the information extracted can be then be dependant on both T2 and T1 (or Diffusion)). The acquired NMR data can be compressed and the compressed NMR data can be analyzed using a Butler-Read-Dawson optimization method.
  • According to one or more aspects of the disclosed subject matter, a method is described for performing a NMR measurement on a porous media wherein at least one NMR measurement parameter is used; obtaining a decay signal from the media based on the NMR measurement parameter; altering one of the at least one NMR measurement parameter and repeating these steps. The decay signal can be dependent on the relaxation parameter T2. The at least one NMR measurement parameter can be selected from the group consisting of a NMR relaxation parameter T2, a NMR relaxation parameter T1 and a molecular diffusion coefficient. Data can be obtained from the decay signal. The data obtained can depend on one or more of the NMR parameters from the group consisting of the NMR relaxation parameter T1, NMR relaxation parameter T2 and the molecular diffusion coefficient. Steps in the method can be repeated to 3 more dimensions.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a representative diagram of a prior art CPMG sequence for T2 analysis;
  • FIG. 2 is a representative diagram of a prior art inversion recovery sequence for T1 analysis;
  • FIG. 3 is a diagram of a prior art inversion recovery CPMG sequence;
  • FIG. 4 is a diagram of a two dimensional map of a final result of the method according to the present invention;
  • FIG. 5 is a flow diagram of steps according to one or more embodiments of the present invention, and
  • FIG. 6 is a schematic diagram of 1D processing steps according to one or more embodiments of the method of the present invention.
  • DETAILED DESCRIPTION
  • Referring to FIG. 3, a NMR measurement inversion recovery CPMG sequence can be used to acquire a plurality of NMR measurements and to systematically vary an NMR measurement parameter, in this case the delay time, T1. The number of NMR measurements made will vary depending upon the requirement to have enough data and the duration of the measurement period. Suitable conventional NMR signal acquisition equipment can be used to make the NMR measurements. It will be understood by those skilled in the art that other prior art pulse sequences can also be used for the same purpose.
  • After each NMR measurement in a plurality of NMR measurements, the decaying NMR signal, S(t), obtained is related to the following equation:
  • S ( t ) = i = 1 N A ( i ) - t T 2 ( i ) ( 3 )
  • Equation (3) can be solved by minimizing the following equation:
  • Error = t = TE t = j * TE ( m ( t ) - i = 1 N A ( i ) - t T 2 ( i ) ) 2 + α i = 1 N A ( i ) 2 ( 4 )
  • where A(i) is the amplitude of each exponential decay component, T2(i), t is time, TE is the CPMG echo time, N is the number of exponential decay components, and α is a smoothing coefficient used in the fitting. This equation can be rewritten to use a kernel of:
  • Kernel ( t , T 2 ( i ) ) = - t T 2 ( i ) ( 5 )
  • This simplifies the error Equation (4) to:
  • Error = t = TE t = j * TE ( m ( t ) - i = 1 N A ( i ) Kernel ( t , T 2 ( i ) ) ) 2 + α i = 1 N A ( i ) 2 ( 6 )
  • The advantage of using a kernel is that it simplifies computation in a computer algorithm. It will be understood by those skilled in the art that computational aspects of the present invention can be computer implemented and performed using a general purpose computer programmed for the purpose. The method of one or more embodiments of the present invention can be stored on non-transitory computer readable memory (such as but not limited to CDs, hard drives, and memory sticks) as statement and instructions for execution by a computer to carry out the method.
  • Upon completion of the plurality of NMR measurements and relating the resulting data to Equation (3), the data is reordered into a series of one dimensional (“1D”) datasets In one embodiment, the first point in each analyzed data set forms the first reordered dataset. These reordered datasets are analyzed one by one using the known equation representing the pulse sequence that created by the variation in NMR measurement parameter. In the case of the pulse sequence shown in FIG. 2 this equation is:
  • S ( t ) = i = 1 N A ( i ) ) ( 1 - 2 - t T 1 ( i ) ) ( 7 )
  • The resultant data obtained by solving equation (S) forms a two dimensional (“2D”) result which can be analyzed to look for differences in the parameters in Equation (1) at different values from Equation (2). See FIG. 4 for an example of the result. In this schematic contour plot representation of a result, the resultant value is converted into an image intensity and plotted at an x-y coordinate equal to the parameter from equation (1) and the parameter from Equation (2). The two contour lines 2 and 4 in the image represent different image intensities. While in this example, the T2 parameter is used for the 1st dimension and T1 for the second dimension, this can be reversed. The flow diagram of FIG. 5 shows steps of one more embodiments of a method according to the present invention. The diagram in FIG. 6 shows the number of 1D processing steps depicted by the arrows. Note that the order of the processing is unimportant as long as all the horizontal processing steps are completed before the vertical steps (or vice versa). In the example above the horizontal processing steps are the solutions to Equation (1) and the vertical are the solutions to Equation (2).

Claims (17)

1. A method of extracting information about a system comprising:
a. performing a NMR measurement;
b. acquiring NMR data from the measurement;
c. expressing the NMR data using a kernel of one dimension;
d. analyzing the data to extract information;
e. repeating steps a. through d., changing one variable to modify the NMR data each time steps a. through d. are repeated;
f. reordering data obtained from step e. to form a one dimensional kernel across the systematically changed variable in step e, and
g. analyzing the data from step f. to extract information.
2. The method of claim 1 further comprising compressing the NMR data.
3. The method of claim 2 where the compressed NMR data are analyzed using a Butler-Read-Dawson optimization method.
4. The method of claim 1 where the analyzed data is presented in the form of a two dimensional map or image.
5. The method of claim 1 wherein the system is porous media.
6. The method of claim 5 wherein the NMR data acquired in step b. is a decaying signal dependent on the relaxation parameter T2.
7. The method of claim 6 wherein the information extracted in step d. is the NMR relaxation parameter T2.
8. The method of claim 7 wherein the variable in step e. is selected in order that the detected NMR signal depends on a NMR parameter from the group consisting of NMR relaxation parameter T1, NMR relaxation paramater T2 andr the molecular diffusion coefficient.
9. The method of claim 8 wherein the data obtained from step e. depends on one or more of the NMR parameters from the group consisting of the NMR relaxation parameter T1, the NMR relaxation parameter T2 and the molecular diffusion coefficient.
10. The method of claim 7 wherein the variable in step e. is selected from the group consisting of NMR pulse sequence timings, NMR pulse sequence magnetic field gradients and combinations thereof.
11. A method comprising:
a. performing a NMR measurement on a porous media wherein at least one NMR measurement parameter is used;
b. obtaining a decay signal from the media based on the NMR measurement parameter;
c. altering one of the at least one NMR measurement parameter and repeating steps a. and b.
12. The method of claim 11 wherein the decay signal is dependent on the relaxation parameter T2.
13. The method of claim 11 wherein the at least one NMR measurement parameter is selected from the group consisting of a NMR relaxation parameter T2, a NMR relaxation parameter T1 and a molecular diffusion coefficient.
14. The method of claim 11 further comprising obtaining data from the decay signal
15. The method of claim 14 wherein the data obtained depends on one or more of the NMR parameters from the group consisting of NMR relaxation parameter T1, NMR relaxation parameter T2 andr and the molecular diffusion coefficient.
16. The method of claim 11 further comprising further repeating step c. to 3 more dimensions.
17. In a method of making a series of NMR measurements, the improvement comprising varying an NMR measurement parameter after each measurement.
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