Systems, methods and apparatus for analysis of reservoir fluids using surface plasmon resonance

• US 10,254,216 B2
• Filed: 06/30/2017
• Issued: 04/09/2019
• Est. Priority Date: 06/30/2016
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: Sieben, Vincent Joseph, Chau, Kenneth John, Molla, Shahnawaz Hossain, Mostowfi, Farshid, Smythe, Elizabeth Jennings
• Primary Examiner(s): Decenzo, Shawn
• Application Number:
  US15/638,443
• Publication Number:
  US 20180003619A1
• Time in Patent Office: 648 Days
• CPC Class Codes: G01N 2021/258 Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
• CPC Class Codes: G01N 21/05 Flow-through cuvettes G01N21/09 takes precedence; handling fluid samples G01N1/10
• CPC Class Codes: G01N 21/27 using photo-electric detection G01N21/31 takes precedence; circuits for computing concentration logarithmic circuits G06G7/24; photometric circuits in general G01J
• CPC Class Codes: G01N 21/553 and using surface plasmons fluorescence excitation G01N21/648; enhanced Raman G01N21/658
• CPC Class Codes: G01N 33/2835 Specific substances contained in the oils or fuels

Abstract

An optical sensor includes a flow cell permitting flow of a hydrocarbon-based analyte therethrough. A metallic film is disposed adjacent or within the flow cell. At least one optical element directs polychromatic light for supply to an interface of the metallic film under conditions of surface plasmon resonance (SPR) and directs polychromatic light reflected at the interface of the metallic film (which is sensitive to SPR at such interface and thus provides an SPR sensing region within the flow cell) for output to at least one spectrometer that measures spectral data of such polychromatic light. A computer processing system is configured to process the measured spectral data over time as the hydrocarbon-based analyte flows through the flow cell to determine SPR peak wavelength over time and to process the SPR peak wavelength over time to determine at least one property related to phase transition of the analyte.

Claims

1. An optical sensor comprising:

a flow cell that is configured to permit flow of a hydrocarbon-based analyte through the flow cell;

a metallic film disposed adjacent or within the flow cell;

a light source configured to generate polychromatic light;

at least one optical element configured to direct polychromatic light produced by the light source for supply to an interface of the metallic film under conditions of surface plasmon resonance and to direct polychromatic light reflected at the interface of the metallic film for output from the at least one optical element, wherein the polychromatic light reflected at the interface of the metallic film is sensitive to surface plasmon resonance at the interface of the metallic film in order to provide an surface plasmon resonance (SPR) sensing region within the flow cell;

at least one spectrometer operably coupled to the at least one optical element, wherein the at least one spectrometer is configured to measure spectral data of polychromatic light reflected at the interface of the metallic film as output by the least one optical element; and

a computer processing system operably coupled to the at least one spectrometer, wherein the computer processing system is configured to process the spectral data measured by the at least one spectrometer over time as the hydrocarbon-based analyte flows through the flow cell to determine SPR peak wavelength over time, and wherein the computer processing system processes the SPR peak wavelength over time to determine at least one property related to phase transition of the hydrocarbon-based analyte.

2. An optical sensor according to claim 1, wherein:

the at least one optical element comprises a prism disposed adjacent the metallic film.

3. An optical sensor according to claim 2, wherein:

the prism comprises a dove prism.

4. An optical sensor according to claim 2, wherein:

the metallic film is part of a multilayer structure formed on one side of a substrate, wherein the multilayer structure interfaces to the flow cell and the opposite side of the substrate is disposed adjacent the prism.

5. An optical sensor according to claim 4, further comprising:

an index matching fluid disposed between the opposite side of the substrate and the prism.

6. An optical sensor according to claim 1, wherein:

the least one optical element comprises a fiber optic core, wherein the metallic film is bonded to the fiber optic core.

7. An optical sensor according to claim 6, wherein:

the metallic film is part of a multilayer structure bonded to the fiber optic core.

8. An optical sensor according to claim 7, wherein:

the multilayer structure surrounds a lengthwise segment of the fiber optic core; and

the lengthwise segment of the fiber optic core directs polychromatic light to the metallic film of the surrounding multilayer structure for reflection at the interface of the metallic film of the surrounding multilayer structure.

9. An optical sensor according to claim 8, wherein:

the least one optical element further comprises a mirror formed at one end of the fiber optic core, wherein the mirror is configured to return polychromatic light reflected at the interface of the metallic film of the surrounding multilayer structure for output to a spectrometer.

10. An optical sensor according to claim 9, wherein:

the mirror is formed from the same metal as the metallic film of the multilayer structure.

11. An optical sensor according to claim 8, wherein:

the fiber optic core is configured to transmit polychromatic light reflected at the interface of the metallic film of the surrounding multilayer structure for output to a spectrometer.

12. An optical sensor according to claim 6, wherein:

the fiber optic core and metallic film are part of a probe assembly that extends into the flow cell.

13. An optical sensor according to claim 12, wherein:

the probe assembly extends into the flow cell in a direction parallel to the flow through the flow cell.

14. An optical sensor according to claim 12, wherein:

the probe assembly extends into the flow cell in a direction transverse to the flow through the flow cell.

15. An optical sensor according to claim 12, further comprising:

a seal that provides a fluid seal between the probe assembly and the flow cell.

16. An optical sensor according to claim 1, wherein:

the metallic film is part of a multilayer structure that interfaces to the flow cell or that extends into the flow cell.

17. An optical sensor according to claim 1, wherein:

the multilayer structure includes a thin-film stack including a protective layer that covers the metallic film and/or a bonding layer formed under the metallic film.

18. An optical sensor according to claim 17, wherein:

the protective layer is present and comprises Zirconium Dioxide.

19. An optical sensor according to claim 17, wherein:

the bonding layer is present and comprises Titanium.

20. An optical sensor according to claim 1, wherein:

the metallic film comprises gold or silver.

21. An optical sensor according to claim 1, further comprising:

a polarizer coupled to the at least one optical element, wherein the polarizer is configured to split polychromatic light reflected at the interface of the metallic film into an s-polarized beam and a p-polarized beam.

22. An optical sensor according to claim 21, wherein:

the at least one spectrometer comprise a first spectrometer and a second spectrometer, the first spectrometer configured to measure spectral data of the s-polarized beam, and the second spectrometer configured to measure spectral data of the p-polarized beam; and

the computer processing system is operably coupled to the first and second spectrometers and is configured to determine an absorbance spectrum for a given time interval by subtracting spectral data of the s-polarized beam from spectral data of the p-polarized beam.

23. An optical sensor according to claim 22, wherein:

the computer processing system is configured to identify a peak in the absorbance spectrum over time in order to determine the SPR peak wavelength over time.

24. An optical sensor according to claim 1, further comprising:

a fiber splitter that directs polychromatic light produced by the light source for supply to the interface of the metallic film.

25. An optical sensor according to claim 24, wherein:

the fiber splitter directs polychromatic light produced by the light source to a first spectrometer; and

the fiber splitter directs polychromatic light reflected at the interface of the metallic film for output to a second spectrometer.

26. An optical sensor according to claim 25, wherein:

the computer processing system is configured to determine an absorbance spectrum for a given time interval by subtracting spectral data determined by measurements of the first spectrometer from spectral data determined by measurements of the second spectrometer.

27. An optical sensor according to claim 26, wherein:

the computer processing system is configured to identify a peak in the absorbance spectrum over time in order to determine the SPR peak wavelength over time.

28. An optical sensor according to claim 1, wherein:

the hydrocarbon-based analyte is mixture of an asphaltene precipitant and crude oil with varying volume fractions of asphaltene precipitant over time; and

the at least one property related to phase transition of the hydrocarbon-based analyte characterizes asphaltene deposition onset of the crude oil.

29. An optical sensor according to claim 1, wherein:

the computer processing system is further configured to employ a model that relates SPR peak wavelength to a refractive index of the crude oil.

30. An optical sensor according to claim 29, wherein:

the model is calibrated by experiments with mixtures of an asphaltene precipitant and asphaltene solvent at different relative volume fractions such that SPR peak wavelengths produced by the model matches measured SPR peak wavelengths determined by the computer processing system.

31. An optical sensor according to claim 29, wherein:

the computer processing system is further configured to employ a correlation function that relates the refractive index of the crude oil to a density of the crude oil.

32. An optical sensor according to claim 1, wherein the at least one property related to phase transition of the hydrocarbon-based analyte is associated with at least one of:

i) detection of the formation of vapor or liquid phases of the hydrocarbon-based analyte induced by temperature and/or pressure changes;

ii) detection of liquid condensation from hydrocarbon vapors induced by temperature and/or pressure changes;

iii) detection of hydrate formation induced by temperature and/or pressure changes;

iv) detection of scaling or inorganic precipitation induced by composition, temperature and/or pressure changes;

v) detection of asphaltene onset induced by composition, temperature and/or pressure or changes; and

vi) sample fluid typing by means of measuring the direction and/or magnitude of the SPR shift when undergoing phase change.

33. An optical sensor according to claim 1, further comprising:

a pressure control system for controlling pressure of the hydrocarbon-based analyte flowing through the flow cell over time.

34. An optical sensor according to claim 33, wherein:

the pressure control system is configured to vary pressure conditions of the hydrocarbon-based analyte flowing through the flow cell over one or more time intervals.

35. An optical sensor according to claim 33, wherein:

the pressure control system is configured to maintain constant pressure conditions of the hydrocarbon-based analyte flowing through the flow cell over one or more time intervals.

36. An optical sensor according to claim 1, further comprising:

a temperature control system for controlling temperature of the hydrocarbon-based analyte flowing through the flow cell over time.

37. An optical sensor according to claim 36, wherein:

the temperature control system is configured to vary temperature conditions of the hydrocarbon-based analyte flowing through the flow cell over one or more time intervals.

38. An optical sensor according to claim 36, wherein:

the temperature control system is configured to maintain constant temperature pressure conditions of the hydrocarbon-based analyte flowing through the flow cell over one or more time intervals.