Optical sensors using surface plasmon resonance to determine at least one property relating to phase change of a hydrocarbon-based analyte

• US 10,281,397 B2
• Filed: 11/10/2016
• Issued: 05/07/2019
• Est. Priority Date: 11/10/2015
• 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, Libby, Cailan, Al-Shakhs, Mohammed, Mostowfi, Farshid, Andersen, Simon Ivar, Smythe, Elizabeth Jennings
• Primary Examiner(s): Nguyen, Sang H
• Application Number:
  US15/348,721
• Publication Number:
  US 20170131204A1
• Time in Patent Office: 908 Days
• CPC Class Codes: G01N 2021/1761 A physical transformation being implied in the method, e.g. a phase change
• CPC Class Codes: G01N 21/0332 with temperature control control of temperature G05D23/00; cryostats F17C3/08
• CPC Class Codes: G01N 21/553 and using surface plasmons fluorescence excitation G01N21/648; enhanced Raman G01N21/658
• CPC Class Codes: G01N 25/02 by investigating changes of state or changes of phase; by investigating sintering investigating or analysing oils or hydrocarbon fluids by measuring cloud point or pour point G01N33/2811
• CPC Class Codes: G01N 33/28 Oils , i.e. hydrocarbon liquids edible oils or edible fats G01N33/03
• CPC Class Codes: G01N 33/2823 Raw oil, drilling fluid or polyphasic mixtures

Abstract

An optical sensor and corresponding method of operation can detect a phase transition and/or related property of a hydrocarbon-based analyte. The optical sensor includes an optical element with a metallic film coupled or integral thereto, with a sample chamber holds the hydrocarbon-based analyte such that the hydrocarbon-based analyte is disposed adjacent the metallic layer. The optical sensor further includes a light source configured to direct light through the optical element such that the light is reflected by the metallic layer under conditions of surface plasmon resonance. The optical sensor analyzes the reflected light to detect a phase transition and/or related property of a hydrocarbon-based analyte.

Claims

1. An optical sensor comprising:

a sample chamber configured to hold a hydrocarbon-based analyte;

a temperature control element configured to regulate temperature of the hydrocarbon-based analyte in the sample chamber;

a pressure control element configured to regulate pressure of the of the hydrocarbon-based analyte in the sample chamber;

a metallic film disposed adjacent the sample chamber;

a light source configured to generate light;

an optical element configured to direct light produced by the light source to the metallic film under conditions of surface plasmon resonance and to direct light reflected at the interface of the metallic film for output from the optical element, such that the light reflected at the interface of the metallic film is sensitive to surface plasmon resonance at the interface of the metallic film;

an optoelectronic device configured to (a) receive light reflected at the interface of the metallic film as directed by the optical element and (b) generate a corresponding electrical signal; and

a computer processing system configured to generate and store data based on the electrical signal generated by the optoelectronic device for a number of test measurements at variable conditions of the hydrocarbon-based analyte in the sample chamber as controlled by the temperature control element and the pressure control element, and wherein the computer processing system is configured to process the data 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 property related to phase transition of the hydrocarbon-based analyte is induced by at least one of;

change in temperature of the hydrocarbon-based analyte, change in pressure of the hydrocarbon-based analyte, and change in composition of the hydrocarbon-based analyte; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte specifies temperature and/or pressure conditions for a phase transition of the hydrocarbon-based analyte.

3. An optical sensor according to claim 1, wherein the at least one property related to phase transition of the hydrocarbon-based analyte specifies temperature and/or pressure conditions for a phase transition of the hydrocarbon-based analyte.

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

the temperature control element includes at least one of (a) a heat exchanger, (b) a thermo-electric Peltier device, and (c) a heat sink.

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

the optical element comprises a prism that directs light produced by the light source to the metallic film and that directs light reflected at the interface of the metallic film for output from the prism.

6. An optical sensor according to claim 5, wherein:

the light source comprises a monochromatic light source that produces monochromatic light;

the sample chamber, the prism and the at least one temperature control element are part of a thermally-controlled assembly that is configured for controlled rotational movement of the thermally-controlled assembly relative to the monochromatic light source in order to vary angle of incidence of monochromatic light on the interface of the metallic film; and

the optoelectronic device comprises a photodetector that is configured for controlled linear movement along a trajectory that maintains alignment of the photodetector with center of a reflected light beam that is output from the prism during controlled rotational movement of the thermally-controlled assembly relative to the monochromatic light source.

7. An optical sensor according to claim 6, further comprising:

a mechanical chopper disposed in an optical path between the monochromatic light source and the prism, wherein the mechanical chopper is configured to modulate the monochromatic light produced by the monochromatic light source at a predetermined frequency for supply to the prism; and

a lock-in amplifier that processes an electrical signal output of the photodetector, wherein operation of the lock-in amplifier is coordinated with the predetermined frequency of light modulation performed by the mechanical chopper.

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

the computer processing system is configured to generate and store intensity data based on the electrical signal generated by the photodetector as a function of angular position of the thermally-controlled assembly relative to the monochromatic light source during controlled rotational movement of the thermally-controlled assembly relative to the monochromatic light source for the number of test measurements at variable conditions of the hydrocarbon-based analyte in the sample chamber as controlled by the at least one temperature control element and the at least one pressure control element, wherein the intensity data characterizes intensity of light reflected at the interface of the metallic film during controlled rotational movement of the thermally-controlled assembly relative to the monochromatic light source, and wherein the computer processing system processes the intensity data as a function of angular position of the thermally-controlled assembly relative to the monochromatic light source to determine the at least one property related to phase transition of the hydrocarbon-based analyte.

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

the intensity data corresponding to different angular positions of the thermally-controlled assembly relative to the monochromatic light source is evaluated to determine the at least one property related to phase transition of the hydrocarbon-based analyte.

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

the at least one property related to phase transition of the hydrocarbon-based analyte is determined based on at least one of the following;

i) a temperature condition and/or pressure condition corresponding to a local minima or dip in the intensity data as a function of the angular position of the thermally-controlled assembly relative to the monochromatic light source;

ii) a temperature condition and/or pressure condition corresponding to an abrupt change to slope or shape of a local minima or dip in the intensity data as a function of the angular position of the thermally-controlled assembly relative to the monochromatic light source;

iii) a temperature condition and/or pressure condition corresponding to an abrupt change in the minimum of the intensity data over the angular positions of the thermally-controlled assembly as a function of temperature or pressure;

iv) a temperature condition and/or pressure condition corresponding to an abrupt change in the intensity data at a plurality of angular positions of the thermally-controlled assembly as a function of temperature or pressure;

v) a temperature condition and/or pressure condition corresponding to an abrupt change in the angle of minimum intensity data over the angular positions of the thermally-controlled assembly relative to the monochromatic light as a function of temperature or pressure; and

vi) a temperature condition and/or pressure condition corresponding to a signal metric derived from the intensity data over the angular positions of the thermally-controlled assembly relative to the monochromatic light as a function of temperature or pressure.

11. An optical sensor according to claim 5, wherein:

the light source comprises a polychromatic light source that produces polychromatic light;

the sample chamber, the prism and the at least one thermal control element are part of a thermally-controlled assembly; and

the optoelectronic device comprises a spectrometer that is configured to receive polychromatic light reflected from the metallic film.

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

the computer processing system is configured to generate and store spectral data based on the electrical signals generated by the spectrometer for the number of test measurements at variable conditions of the hydrocarbon-based analyte in the sample chamber as controlled by the at least one temperature control element and the at least one pressure control element, and wherein the computer processing system is configured to process the spectral data to determine the at least one property related to phase transition of the hydrocarbon-based analyte.

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

The computer processing system is configured to evaluate spectral data to determine the at least one property related to phase transition of the hydrocarbon-based analyte.

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

The computer processing system is configured to determine the at least one property related to phase transition of the hydrocarbon-based analyte based on temperature and/or pressure conditions that produce a shift in a local minima or dip in the spectral data or temperature and/or pressure conditions that produce a signal metric in the spectral data.

15. An optical sensor according to claim 1, wherein at least one of (a) the sample chamber has a fixed volume and (b) the sample chamber is part of a flow-thru cell.

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

the metallic film is formed (a) as a coating on the optical element or (b) as a coating on a substrate that is disposed adjacent the optical element.

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

a layer of protective material covers the metallic film such that the hydrocarbon-based analyte does not directly contact the metallic film.

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

an electrical circuit that is electrically coupled to the metallic film for controlled resistive heating of the metallic film.

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

the electric circuit is configured to provide pulsed-mode operation including on cycles where the metallic film is heating by resistive heating and off cycles where the metallic film is not heated by resistive heating.

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

the at least one property related to phase transition of the hydrocarbon-based analyte is derived from test measurements with i) pressure or pressure differential of the hydrocarbon-based analyte in the sample chamber at a controlled pressure and ii) temperature of the hydrocarbon-based analyte in the sample chamber controlled over a range of set point temperatures.

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

the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where components that are dissolved in the hydrocarbon-based analyte precipitate and form liquids or solids; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte is a Wax Appearance Temperature (WAT) where wax components that are dissolved in the hydrocarbon-based analyte first precipitate and form solid material; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where components of the hydrocarbon-based analyte transition from a gas phase to a liquid phase; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where components of the hydrocarbon-based analyte transition from a liquid phase to a gas phase; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte is bubble point temperature and/or pressure conditions where vapor forms from the hydrocarbon-based analyte or where vapor dissolve into the hydrocarbon-based analyte as induced by changes in temperature, pressure and/or composition of the hydrocarbon-based analyte; and

/or the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where hydrates form from the hydrocarbon-based analyte as induced by changes in temperature, pressure and/or composition of the hydrocarbon-based analyte; and

/or

the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where scale or other inorganic material precipitate from the hydrocarbon-based analyte as induced by changes in temperature, pressure and/or composition of the hydrocarbon-based analyte.

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

the at least one property related to phase transition of the hydrocarbon-based analyte is a temperature condition and/or pressure condition where asphaltenes in the hydrocarbon-based analyte precipitate as liquid or solid, and/or deposit as a liquid or solid film as induced by changes in temperature, pressure and/or composition of the hydrocarbon-based analyte.

23. A downhole tool that can be conveyed in a wellbore that traverses a subterranean formation and configured to sample formation fluid obtained from the subterranean formation, the downhole tool comprising:

the optical sensor of claim 1 for determining at least one property related to phase transition of the formation fluid.

24. A wellsite that produces fluid obtained from a subterranean formation, wherein the wellsite includes the optical sensor of claim 1 for determining at least one property related to phase transition of the produced fluid.

25. A method of optical sensing comprising:

loading a sample chamber with a hydrocarbon-based analyte and a metallic film disposed adjacent the sample chamber;

with the hydrocarbon-based analyte in the sample chamber, directing light produced by a light source to the metallic film under conditions of surface plasmon resonance and directing light reflected at the interface of the metallic film to an optoelectronic device configured to (a) receive the light reflected at the interface of the metallic film and (b) generate a corresponding electrical signal, wherein the light reflected at the interface of the metallic film is sensitive to surface plasmon resonance at the interface of the metallic film;

using a computer processing system to generate and process data based on the electrical signal to detect a phase transition or related property with respect to the hydrocarbon-based analyte; and

wherein the computer processing system generates data based on the electrical signal generated by the optoelectronic device for a number of test measurements at variable conditions of the hydrocarbon-based analyte in the sample chamber as controlled by at least one temperature control element and at least one pressure control element.

26. A method according to claim 25, wherein:

the optoelectronic device comprises a photodetector;

the computer processing system generates and stores intensity data derived from the output of the photodetector; and

the computer processing system processes the intensity data to detect a phase transition or related property with respect to the hydrocarbon-based analyte.

27. A method according to claim 25, wherein:

the optoelectronic device comprises a spectrometer;

the computer processing system acquires and stores spectral data generated by the spectrometer; and

the computer processing system processes the spectral data to detect a phase transition or related property with respect to the hydrocarbon-based analyte.