ACTIVE SURFACE CLEANING FOR A SENSOR

Abstract

An integrated approach for cleaning an active surface of a petrochemical sensor. Sensors in the petrochemical industry are often deployed in locations where they are prone to fouling. By heating the active surface fouling substances may be removed from the active surface. Heating the surface above a supercritical point of a fluid being sensed may create a fluid that may serve to clean the active surface. Limiting the duration of the applied heating and/or pulsing the heating may mitigate adverse effects of use of high temperatures. A doped active surface, such as a doped diamond window may be designed to have conductive areas in the window that may be used for resistive heating of the window.

Claims

1. A sensor for monitoring a species which is a component of a fluid, the sensor including: an internal reflection window configured in use for contacting with the fluid; a mid-infrared light source configured to direct a beam of mid-infrared radiation into the internal reflection window and produce attenuated internal reflection of the beam at an interface between the internal reflection window and the fluid; a first narrow bandpass filter configured to receive from the internal reflection window the attenuated internal reflection of the beam and to filter the received attenuated internal reflection of the beam, wherein the first narrow bandpass filter is configured to preferentially transmit mid-infrared radiation over a band of wavelengths corresponding to an absorbance peak of the species; an infrared detector for detecting filtered mid-infrared radiation transmitted through the first narrow bandpass filter; a processor arrangement, operably coupled to the infrared detector and configured to measure an intensity of the detected mid-infrared radiation transmitted through the first narrow bandpass filter and determine from the measured intensity an amount of the species in the fluid; and a heater configured to locally heat the internal reflection window to clean the surface of the internal reflection window in contact with the fluid, wherein the internal reflection window includes a conductive or semiconductive material and the heater comprises an electrical power supply for sending a current through the internal reflection window to induce resistive heating of the internal reflection window.

2. The sensor according to claim 1, wherein the heater heats the internal reflection window to a peak temperature of at least about 400° C.

3. The sensor according to claim 1, wherein the heater maintains a peak temperature for less than one microsecond.

4. The sensor according to claim 1, further comprising: a second narrow bandpass filter configured to transmit mid-infrared radiation over a band of wavelengths corresponding to a reference portion of the absorbance spectrum of the fluid, wherein the or a further infrared detector is configured to detect filtered mid-infrared radiation transmitted through the second narrow bandpass filter, and wherein the processor arrangement is configured to measure a reference intensity of the detected mid-infrared radiation transmitted through the second narrow bandpass filter and use the measured reference intensity in the determination of the amount of the species in the fluid.

5. The sensor according to claim 1, comprising: a plurality of the first narrow bandpass filters, each configured to transmit mid-infrared radiation over a band of wavelengths corresponding to an absorbance peak of a respective species, the or a respective further infrared detector configured to detect the filtered mid-infrared radiation transmitted through each first narrow bandpass filter, and the processor arrangement configured to measure the intensity of the detected mid-infrared radiation transmitted through each first narrow bandpass filter and determine from the measured intensity an amount of each species in the fluid.

6. The sensor according to claim 5, wherein the determined amounts of the species in the fluid is in the form of a ratio of the concentrations of the species.

7. The sensor according to claim 1, wherein the beam of mid-infrared light is pulsed.

8. The sensor according to claim 1, wherein the internal reflection window is a diamond internal reflection window or a sapphire internal reflection window.

9. The sensor according to claim 1 which is configured for use downhole.

10. The sensor according to claim 1 which is adapted for monitoring one or more of a hydrocarbon species which is a component of a hydrocarbon liquid, a hydrate inhibitor species which is dissolved in a liquid, or a mineral acid species which is dissolved in a liquid.

11. (canceled)

12. (canceled)

13. The sensor according to claim 1 which is adapted for monitoring CO.sub.2 concentration in the fluid, the sensor having three first narrow bandpass filters corresponding to respective absorbance peaks of water, oil and CO.sub.2, wherein the processor arrangement determines an amount of CO.sub.2 notwithstanding whether the fluid contacting the internal reflection window is a liquid water-based phase, a liquid oil-based phase, a mixture of liquid water and liquid oil-based phases, or a gas phase.

14. (canceled)

15. A borehole or pipeline sensor including an optical or electrical sensing element that in use contacts a fluid being sensed, the sensor comprising: a heater configured to locally heat the sensing element to clean the surface of the element in contact with the fluid.

16. The sensor of claim 15, further comprising a processor configured to control the heater, wherein the processor controls the heater to heat the internal reflection window to a temperature in excess of about 400° C.

17. (canceled)

18. The sensor of claim 15, wherein the processor controls the heater to heat the internal reflection window to a peak temperature and maintain the internal reflection window at the peak temperature for a period of less than about a microsecond.

19. (canceled)

20. The sensor of claim 16, wherein the processor controls the heater to heat the internal reflection window for a period of the order of seconds, tenths of seconds, hundredths of seconds or microseconds.

21. The sensor of claim 15, wherein the window comprises diamond or sapphire.

22. A well tool including the sensor of claim 1.

23-36. (canceled)

37. The sensor according to claim 1, wherein the first narrow bandpass filter comprises a substrate having opposing surfaces, and wherein alternating dielectric layers of high and low refractive index are stacked on the opposing surfaces of the substrate.

38. The sensor according to claim 37, wherein the high refractive index layers are formed of one or more of PbTe, PbSe, PbS, or Ge.

39. The sensor according to claim 37, wherein the low refractive index layers are formed of one or more of ZnS or ZnSe.

40. The sensor according to claim 37, wherein each layer in the stacks of alternating layers of high and low refractive index has an optical thickness of about one quarter wavelength

41. The sensor according to claim 37, wherein the first narrow bandpass filter is configured such that its wavelength transmission band is substantially temperature invariant over all temperatures in the range of about 25° C. to about 150 ° C.

42. A method for monitoring a species which is a component of a fluid, the method comprising: contacting an internal reflection window with the fluid; using a mid-infrared light source to direct a beam of mid-infrared radiation into said window and produce attenuated internal reflection of the beam at an interface between the window and the fluid: passing the attenuated internal reflection of the beam through a narrow bandpass filter, wherein the narrow bandpass filter is configured to filter the received attenuated internal reflection of the beam by preferentially transmitting mid-infrared radiation over a band of wavelengths corresponding to an absorbance peak of the species; detecting filtered mid-infrared radiation transmitted through the first filter; measuring an intensity of the detected mid-infrared radiation transmitted through the first filter; determining from the measured intensity an amount of the species in the fluid; and heating the window to clean the surface of the window in contact with the fluid.

43. The method according to claim 42, wherein the first narrow bandpass filter comprises a substrate having opposing surfaces, and wherein alternating dielectric layers of high and low refractive index are stacked on the opposing surfaces of the substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which:

[0047] FIG. 1 shows schematically, in accordance with embodiments of the present disclosure: (a) a mid-infrared sensor, and (b) the sensor implemented as a module in a toolstring;

[0048] FIG. 2 shows schematically a narrow bandpass filter based on Fabry-Perot interferometry, in accordance with an embodiment of the present disclosure;

[0049] FIG. 3 shows variation of dλ.sub.m/λ.sub.mdT for a suite of filters fabricated with ZnSe as the low refractive index material and PbTe as the high refractive index material, in accordance with an embodiment of the present disclosure;

[0050] FIG. 4 shows plots of transmissivity against wavelength at a range of temperatures from 25 to 200° C. for (a) a PbTe-based filter having a pass band centred at 4.26 μm, and (b) a PbTe-based filter having a pass band centred at 12.1 μm, in accordance with embodiments of the present disclosure;

[0051] FIG. 5 shows (a) a reference intensity spectrum I.sub.0 obtained from a fluid not containing a given species, (b) an intensity spectrum I obtained from the fluid containing the species, and (c) the absorbance spectrum of the species;

[0052] FIG. 6 shows intensity spectra obtained for dodecane dissolved in deuterated chloroform for increasing concentrations of dodecane, the spectra being superimposed with transmissivity plots for a first filter having a pass band of 3000 to 2800 cm.sup.−1, and a second filter having a pass band of 2000 to 1800 cm.sup.−1;

[0053] FIG. 7 shows a plot of modified absorbance A′ against hydrocarbon content for dodecane dissolved in deuterated chloroform;

[0054] FIG. 8 shows a plot of absorbance against dissolved CO.sub.2 concentration in water or hydrocarbon;

[0055] FIG. 9 shows absorbance spectra of the n-alkane series C.sub.5 to C.sub.17;

[0056] FIG. 10 shows plots of concentration of CH.sub.2 groups and concentration of CH.sub.3 groups against carbon chain length for the n-alkane series C.sub.5 to C.sub.17;

[0057] FIG. 11 shows experimentally determined plots of absorbance against concentration of the respective group for n-alkane 2957 cm.sup.−1 CH.sub.3 peak, 2853 cm.sup.−1 CH.sub.2 peak and 2922 cm.sup.−1 CH.sub.2 peak;

[0058] FIG. 12 shows mid-infrared absorbance spectra of a number of crude oils, with C.sub.7 and C.sub.10 alkane spectra also shown for reference;

[0059] FIG. 13 shows the mid-infrared absorbance spectra of the crude oils of FIG. 12 superimposed with the spectra for three common base oils;

[0060] FIG. 14 shows again the mid-infrared absorbance spectra of the crude oils of FIG. 12 superimposed with the spectra for two synthetic base oils;

[0061] FIG. 15 shows a graph of CH.sub.2/CH.sub.3 ratio against CH.sub.2 group concentration with crude oils plotted as squares and base oils as triangles, and also a curve for n-alkanes;

[0062] FIG. 16 shows mid-infrared absorbance spectra of (a) monoethylene glycol in water, (b) methanol in water, and (c) ethanol in water, for different inhibitor concentrations from 0 to 100 vol %;

[0063] FIG. 17 shows plots of absorbance against inhibitor concentration for (a) monoethylene glycol in water, (b) methanol in water, and (c) ethanol in water;

[0064] FIG. 18 shows mid-infrared absorbance spectra of (a) 50 vol % monoethylene glycol in water and in water saturated with NaCl, (b) 50 vol % methanol in water and in water saturated with NaCl, and (c) 50 vol % ethanol in water and in water saturated with NaCl;

[0065] FIG. 19 shows mid-infrared absorbance spectra at 50 vol % water of mixtures of monoethylene glycol and methanol, with the mixtures varying from 100% monoethylene glycol to 100% methanol;

[0066] FIG. 20 shows plots of absorbance against concentration for respectively monoethylene glycol (diamonds) based on the leftmost peak of FIG. 19 and methanol (squares) based on the rightmost peak of FIG. 19;

[0067] FIG. 21 shows mid-infrared absorbance spectra of polyvinylpyrrolidone in water, for different inhibitor concentrations from 0 to 5 wt %;

[0068] FIG. 22 shows a plot of absorbance against inhibitor concentration for polyvinylpyrrolidone in water;

[0069] FIG. 23 shows mid-infrared absorbance spectra of 5 wt % polyvinylpyrrolidone in water and in water saturated with NaCl

[0070] FIG. 24 shows mid-infrared absorbance spectra of HCl in water, for different HCl concentrations from 0 to 40 wt %;

[0071] FIG. 25 shows a plot of absorbance against HCl concentration for HCl in water;

[0072] FIG. 26 shows mid-infrared absorbance spectra of DCl in D.sub.2O, for different DCl concentrations from 0 to 35 wt %;

[0073] FIG. 27 shows a plot of absorbance against DCl concentration for DCl in D.sub.2O;

[0074] FIG. 28 shows mid-infrared absorbance spectra of 4.2 M HCl in water, 4.7 M HBr in water and 4.5 M HI in water;

[0075] FIG. 29 shows the plots of absorbance against acid concentration for HCl, HBr and HI in water;

[0076] FIG. 30 shows (a) a mid-infrared absorbance spectrum for a water phase and CO.sub.2, and (b) a corresponding plot of absorbance against CO.sub.2 concentration for CO.sub.2 in H.sub.2O;

[0077] FIG. 31 shows (a) a mid-infrared absorbance spectrum for an oil phase and CO.sub.2, and (b) a corresponding plot of absorbance against CO.sub.2 concentration for CO.sub.2 in oil;

[0078] FIG. 32 shows a mid-infrared absorbance spectrum for a water phase, an oil phase and CO.sub.2; and

[0079] FIG. 33 shows a plot of absorbance against CO.sub.2 concentration for CO.sub.2 in gas phase.

[0080] In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.

DETAILED DESCRIPTION

[0081] The ensuing description provides preferred exemplary embodiment(s) only, and is not intended to limit the scope, applicability or configuration of the invention. Rather, the ensuing description of the preferred exemplary embodiment(s) will provide those skilled in the art with an enabling description for implementing a preferred exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements without departing from the scope of the invention.

[0082] Specific details are given in the following description to provide a thorough understanding of the embodiments. However, it will be understood by one of ordinary skill in the art that embodiments maybe practiced without these specific details. For example, well-known circuits, processes, algorithms, structures, and techniques may be shown without unnecessary detail in order to avoid obscuring the embodiments.

[0083] Also, it is noted that the embodiments may be described as a process which is depicted as a flowchart, a flow diagram, a data flow diagram, a structure diagram, or a block diagram. Although a flowchart may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be re-arranged. A process is terminated when its operations are completed, but could have additional steps not included in the figure. A process may correspond to a method, a function, a procedure, a subroutine, a subprogram, etc. When a process corresponds to a function, its termination corresponds to a return of the function to the calling function or the main function.

[0084] Moreover, as disclosed herein, the term “storage medium” may represent one or more devices for storing data, including read only memory (ROM), random access memory (RAM), magnetic RAM, core memory, magnetic disk storage mediums, optical storage mediums, flash memory devices and/or other machine readable mediums for storing information. The term “computer-readable medium” includes, but is not limited to portable or fixed storage devices, optical storage devices, wireless channels and various other mediums capable of storing, containing or carrying instruction(s) and/or data.

[0085] Furthermore, embodiments may be implemented by hardware, software, firmware, middleware, microcode, hardware description languages, or any combination thereof. When implemented in software, firmware, middleware or microcode, the program code or code segments to perform the necessary tasks may be stored in a machine readable medium such as storage medium. A processor(s) may perform the necessary tasks. A code segment may represent a procedure, a function, a subprogram, a program, a routine, a subroutine, a module, a software package, a class, or any combination of instructions, data structures, or program statements. A code segment may be coupled to another code segment or a hardware circuit by passing and/or receiving information, data, arguments, parameters, or memory contents. Information, arguments, parameters, data, etc. may be passed, forwarded, or transmitted via any suitable means including memory sharing, message passing, token passing, network transmission, etc.

[0086] It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of various embodiments. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. In addition, the present disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. Moreover, the formation of a first feature over or on a second feature in the description that follows may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed interposing the first and second features, such that the first and second features may not be in direct contact.

[0087] FIG. 1(a) shows schematically a mid-infrared sensor having a thermal broad band mid-infrared source 1, a mechanical chopper 2 that pulses a beam 3 of mid-infrared radiation which issues from the source, a diamond window 4, a set of selectively movable first narrow bandpass filters 5 and a second narrow bandpass filter 5′, respective mid-infrared detectors 6 for the filters, and a processor arrangement 7. The sensor is encased in a protective housing which allows the sensor to be deployed downhole, the window 4 being positioned for contact with the fluid to be monitored. Mid-infrared waveguides (not shown) optically connect the source, window and the detectors. Suitable waveguides can be formed from optical fibres (e.g. hollow fibres or chalcogenide fibres), solid light pipes (e.g. sapphire pipes), or hollow light pipes (e.g. air or vacuum filled) with a reflective (e.g. gold) coating.

[0088] As the detector 6 changes its output with its temperature, even small changes in temperature can cause a large drift in signal output. However, pulsing the beam 3 allows the output signal of the detector to be frequency modulated, enabling removal of the environmental temperature effects from the signal. More particularly, the environment effects can be largely removed electronically by a high pass filter, because the time constant for environment effects tends to be much longer than the signal frequency. Typically, the detector output is AC-coupled to an amplifier. The desired signal can then be extracted e.g. electronically by lock-in amplification or computationally by Fourier transformation.

[0089] Instead of the thermal source 1 and the mechanical chopper 2, the pulsed beam 3 may be produced e.g. by a pulsable thermal source, light emitting diode or laser source. Pulsing the source in this way can give the same benefit of frequency modulation measurement, plus it can reduce resistive heating effects.

[0090] The beam 3 enters at one edge of the window 4, and undergoes a number of total internal reflections before emerging from the opposite edge. The total internal reflection of the infrared radiation at the fluid side of the window is accompanied by the propagation of an evanescent wave into the fluid. As the fluid preferentially absorbs certain wavelengths, depending on its chemical composition, this causes the emerging beam to have a characteristic variation in intensity with wavelength.

[0091] The window 4 is mechanically able to withstand the high pressures and temperatures typically encountered downhole. It is chemically stable to fluids encountered downhole and is transparent in the mid-IR wavelength region. Candidate materials for the window are diamond and sapphire.

[0092] The first narrow bandpass filters 5 each transmit mid-infrared radiation over a band of wavelengths corresponding to an absorbance peak of a respective species in the fluid, while the second narrow bandpass filter 5′ transmits mid-infrared radiation over a band of wavelengths corresponding to a reference portion of the absorbance spectrum of the fluid. The beam 3 then passes through a selected one of the narrow bandpass filters and is detected at the respective detector 6. Instead of having a plurality of detectors, each movable with its corresponding filter (as indicated by the double-headed arrow), a further option is to have a single detector in front of which the filters are selectively movable.

[0093] The detector 6 can be e.g. semiconductor photo-diodes (particularly in subsea applications), thermopiles or pyroelectric detectors.

[0094] The processor arrangement 7 receives a signal from the respective detector 6, which it processes to measure the intensity of the detected mid-infrared radiation transmitted through each filter 5, 5′, and, as discussed in more detail below, determines therefrom an amount of the respective species in the fluid.

[0095] Also discussed in more detail below, the sensor has a heater 8 which is operable to locally heat the window 4, thereby cleaning the surface of the window in contact with the fluid.

[0096] FIG. 1(b) shows schematically how the sensor can be implemented as a module in a toolstring. The source 1 and chopper 2 are contained in a source unit 9 and filters 5, 5′ and detectors 6 are contained in a detector unit 10. These are located close to the window 4 that is in contact with a tool flowline 11. The sensor is packaged in a protective metal chassis 12 to withstand the high pressure of the fluid in the flowline. The window is sealed into the chassis also to withstand the high pressures, and its packaging ensures no direct source light strays into the detectors.

Narrow Bandpass Filters

[0097] In embodiments of the present disclosure, the narrow bandpass filters 5, 5′ may be based on Fabry-Perot interferometry. As shown in FIG. 2, each filter may have a substrate S of low refractive index and thickness d. On opposing surfaces of the substrate are stacked alternating high-reflectivity dielectric layers of high H and low L refractive index deposited onto the substrate using techniques such as ion-beam sputtering or radical-assisted sputtering. In some embodiments of the present disclosure, each layer in the stacks of alternating layers of high H and low L refractive index has an optical thickness of a quarter wavelength.

[0098] The optical thickness ndcosθ of the substrate S, where n is the refractive index of the substrate, is equal to an integer number of half wavelengths λ.sub.m, where λ.sub.m is the peak transmission wavelength, corresponding approximately to the centre wavelength of the pass band of the filter. The condition for the transmission of radiation of wavelength λ.sub.m through the filter is thus mλ.sub.m/2=ndcosθ, where m is an integer.

[0099] The spectral region of conventional narrow bandpass dielectric filters designed to operate in the mid-infrared spectral regions shifts systematically to longer wavelengths with increasing temperature. The origin of the change in λ.sub.m with temperature is a change in the material properties with temperature of the dielectric materials that comprise the layers of the filter.

[0100] However, an approach described below, in accordance with an embodiment of the present disclosure, provides for the configuration and fabrication of mid-infrared narrow bandpass filters that have substantially temperature invariant optical properties over a wide temperature range.

[0101] The approach can be considered by the design of the filter:

(LH).sup.x1(LL).sup.y1(HL).sup.x2(LL).sup.y2 . . . (LL).sup.yN(HL).sup.xN+1

consisting of a total of y half wavelength spacers (cavities) LL of low refractive index material in N cycles (y=Σy.sub.i), LH being the stacks of x.sub.i quarter wavelength layers of alternating of high and low refractive index material in the N cycles. The reflections wavelength of the quarter wavelength reflector stack (which is the only reflection to undergo constructive interference), irrespective of the values of x.sub.i and N, can be expressed as:

λ.sub.m=2(n.sub.Ld.sub.L+n.sub.Hd.sub.H)

for first order reflections (m=0). The temperature variation of the wavelength in the reflector stack dλ.sub.m/dT|.sub.s can be expressed as:

[00001]$\frac{d.Math..Math.{\lambda }_m}{\mathrm{dT}}.Math.{}_s=2.Math.n_L.Math.d_L\left(C_L+\frac{{\mathrm{dn}}_L}{n_L.Math.\mathrm{dT}}\right)+2.Math.n_H.Math.d_H\left(C_H+\frac{{\mathrm{dn}}_H}{n_H.Math.\mathrm{dT}}\right)$

where C.sub.L and C.sub.H are the coefficients of linear expansion of the low and high refractive index materials, respectively. From eqn.[1] for first order reflection and normal incidence (i.e., m=1 and θ=0°), the corresponding temperature dependence dλ.sub.m/dT|.sub.c of the cavity layer of low refractive index material is given by:

[00002]$\frac{d.Math..Math.{\lambda }_m}{\mathrm{dT}}.Math.{}_c=2.Math.{\mathrm{yn}}_L.Math.d_L\left(C_L+\frac{{\mathrm{dn}}_L}{n_L.Math.\mathrm{dT}}\right)$

noting that y is the total number of half wavelength cavity layers. The total change in wavelength with temperature d□.sub.m/dT|.sub.T is given by the sum of dλ.sub.m/dT|.sub.c and dλ.sub.m/dT|.sub.s:

[00003]$\begin{array}{c}\frac{d.Math..Math.{\lambda }_m}{\mathrm{dT}}.Math.{}_T=2.Math.\left(1+y\right).Math.n_L.Math.d_L\left(C_L+\frac{{\mathrm{dn}}_L}{n_L.Math.\mathrm{dT}}\right)+2.Math.n_H.Math.d_H\left(C_H+\frac{{\mathrm{dn}}_H}{n_H.Math.\mathrm{dT}}\right)\\ \mathrm{or}\\ \frac{d.Math..Math.{\lambda }_m}{.Math.{\lambda }_m.Math.\mathrm{dT}}.Math.{}_T=\left(1+y\right).Math.\left(C_L+\frac{{\mathrm{dn}}_L}{n_L.Math.\mathrm{dT}}\right)+\left(C_H+\frac{{\mathrm{dn}}_H}{n_H.Math.\mathrm{dT}}\right)\end{array}$

noting that n.sub.Ld.sub.L=n.sub.Hd.sub.H at the temperature for which the filter is designed for use. Clearly dλ.sub.m/dT|.sub.T can only be zero if the value of dn/dT for one of the materials is negative. This condition can be fulfilled by high refractive index materials such as PbTe, PbSe or PbS. For close matching of the value of dλ.sub.m/dT|.sub.T to zero, the wavelength dependence of n.sub.i temperature and wavelength dependence of dn.sub.i/dT can be taken into account.

[0102] The condition dλ.sub.m/dT|.sub.T=0 is given approximately by:

[00004]$\frac{{\mathrm{dn}}_H}{n_L.Math.\mathrm{dT}}=-\left(1+y\right).Math.\frac{{\mathrm{dn}}_L}{n_L.Math.\mathrm{dT}}$

noting that C.sub.i is considerably smaller than dn.sub.i/n.sub.idT for most materials used in mid-infrared filters. The term (1+y) can be chosen to satisfy the above expression depending on the choice of low refractive index material. For example, with ZnSe and PbTe for the low and high refractive index materials, respectively, and using the material values of bulk phases n.sub.L=2.43, n.sub.H=6.10, dn.sub.L/dT=6.3×10.sup.−5 K.sup.−1 and dn.sub.H/dT=−2.1×10.sup.−3 K.sup.−1 for λ.sub.m=3.4 □n, the expression is satisfied with y=13.3, i.e., approximately 13 half wavelength cavity layers are required to achieve the condition dλ.sub.m/dT|.sub.T=0.

[0103] There is considerable variation in the values of the material properties (n.sub.H, dn.sub.H/dT, C.sub.H, etc.) that appear in for thin films in a multilayer structure and therefore in the predicted value of dλ.sub.m/λ.sub.mdT or the value of y required to achieve the condition dλ.sub.m/λ.sub.mdT=0. The uncertainty is particularly severe for the value of dn.sub.H/dT for PbTe in view of its magnitude and influence on the value of y. For example, the value of dn/dT for PbTe at λ.sub.m=5 □n has been reported to be −1.5×10.sup.−3 K.sup.−1 by Zemel, J. N., Jensen, J. D. and Schoolar, R. B., “ELECTRICAL AND OPTICAL PROPERTIES OF EPITAXIAL FILMS OF PBS, PBSE, PBTE AND SNTE”, Phys. Rev. 140, A330-A343 (1965), −2.7×10.sup.−3 K.sup.−1 by Piccioli, N., Besson, J. M. and Balkanski, M., “OPTICAL CONSTANTS AND BAND GAP OF PBTE FROM THIN FILM STUDIES BETWEEN 25 AND 300° K.”, J. Phys. Chem. Solids, 35, 971-977 (1974), and −2.8×10.sup.−3 K.sup.−1 by Weiting, F. and Yixun, Y., “TEMPERATURE EFFECTS ON THE REFRACTIVE INDEX OF LEAD TELLURIDE AND ZINC SELENIDE”, Infrared Phys., 30, 371-373 (1990). From the above expression, the corresponding values of y (to the nearest integer) are 9, 17 and 18, respectively.

[0104] In view of the uncertainties in the value of dn/dT for PbTe and therefore the number of low refractive index half wavelength spacers required to achieve dλ.sub.m/dT=0, a more useful approach is to determine the experimental value of dλ.sub.m/dT as a function of the optical thickness of the low refractive index cavities for a suite of filters fabricated by the same method. FIG. 3 shows the variation of dλ.sub.m/λ.sub.mdT for a suite of filters fabricated with ZnSe as the low refractive index material and PbTe as the high refractive index material. The plot shows that a particular value of dλ.sub.m/λ.sub.mdT can be achieved by controlling the ratio of low to high refractive index materials in the filter (i.e., a parameter similar to y in the above expression). FIG. 3 shows that for λ.sub.m<5 μm, the condition dλ.sub.m/λ.sub.mdT=0 is met by a 4:4:4 (i.e., 3 full wavelength or 6 half wavelength cavities (y=6)) filter, while for λ.sub.m>5 □m a 6:4:6 (y=8) filter is required.

[0105] The approach illustrated by FIG. 3 can be used, in accordance with an embodiment of the present disclosure, to fabricate substantially temperature invariant filters over the entire mid-infrared spectral range. In some embodiments of the present disclosure, the substrate may be formed of Si, SiO.sub.2, Al.sub.2O.sub.3, Ge or ZnSe. In some embodiments of the present disclosure, high refractive index layers can be formed of PbTe, PbSe or PbS, although Ge is also an option. In some embodiments of the present disclosure, the low refractive index layers can be formed of ZnS or ZnSe.

[0106] FIG. 4 shows plots of transmissivity against wavelength at a range of temperatures from 25 to 200° C. for (a) a PbTe-based filter having a pass band centred at 4.26 μm with optimum optical matching to the substrate and 3 full wavelength thickness cavities (4:4:4), and (b) a degenerate PbTe-based filter having a pass band centred at 12.1 μm with 3 half wavelength cavities (2:2:2). Similar filters can be produced having pass bands centred at other mid-infrared wavelengths. The value of dλ.sub.m/dT for the λ.sub.m=4.26 □m (4:4:4) filter varies from −0.04 nm/K at 20° C. to +0.03 nm/K at 200° C. and is essentially zero over the temperature range 80-160° C. The value of dλ.sub.m/dT for the λ.sub.m=12.1 □m (2:2:2) filter is −0.21 nm/K, over the temperature range 20-200° C. This allows such filters to deployed downhole, where temperatures can vary from about 25 to 200° C., without the pass band of the filter shifting to such an extent that it no longer corresponds to the absorbance peak of its respective species.

Spectroscopy

[0107] The Beer-Lambert law applied to the sensor of FIG. 1 provides that:

A=−log.sub.10(I/I.sub.0)

where A is the absorbance spectrum by a species in the fluid having an absorbance peak at a wavelengths corresponding to the pass band of the filter 5, I is the intensity spectrum of the infrared radiation detected by the detector 6, and I.sub.0 is a reference intensity spectrum. For example, FIG. 5 shows (a) a reference intensity spectrum I.sub.0 obtained from a fluid not containing a given species, (b) an intensity spectrum I obtained from the fluid containing the species, and (c) the absorbance spectrum of the species.

[0108] FIG. 6 shows intensity spectra obtained for dodecane dissolved in deuterated chloroform for increasing concentrations of dodecane. With increasing hydrocarbon content there is increased absorption in a first wavenumber range of 3000 to 2800 cm.sup.−1. Conversely, the increasing hydrocarbon content has substantially no effect on absorption in a second wavenumber range of 2000 to 1800 cm.sup.−1. The second range can thus be used as the reference to the first range. Superimposed on FIG. 6 are transmissivity plots for a first filter having a pass band of 3000 to 2800 cm.sup.−1, and a second filter having a pass band of 2000 to 1800 cm.sup.−1. Two spectra are thus, in effect, detected by the filters, the first spectrum being the unfiltered spectrum multiplied by the transmissivity of the first filter and the second sub-spectrum being the unfiltered spectrum multiplied by the transmissivity of the second filter. The pass band areas of the spectra (as determined by the strengths of the signals received by the photodiode detectors), correspond to respective intensity measurements BA and BA.sub.0. These are thus used to calculate a modified absorbance A′ for dodecane dissolved in deuterated chloroform which is ln(BA/BA.sub.0).

[0109] FIG. 7 shows a plot of modified absorbance A′ against hydrocarbon content for dodecane dissolved in deuterated chloroform. The plot exhibits an approximately linear relationship between A′ and hydrocarbon content.

[0110] Other species can be monitored in this way. For example, FIG. 8 shows a plot of absorbance against dissolved CO.sub.2 concentration in water or hydrocarbon under the high partial pressures and temperatures typical of oil field wellbore conditions.

Hydrocarbon Characterisation

[0111] A mid-infrared sensor, of the type discussed above, may be used to characterise hydrocarbons downhole. The ability of the sensor to operate under a full range of downhole temperatures is particularly advantageous. The sensor may be deployed, for example, in a drilling, production well or wireline sampling tool.

[0112] FIG. 9 shows absorbance spectra of the n-alkane series C.sub.5 to C.sub.17. The mid-infrared spectrum is largely determined by CH.sub.2 and CH.sub.3 groups. FIG. 10 shows plots of concentration of CH.sub.2 groups and concentration of CH.sub.3 groups against carbon chain length. With increasing chain length, the relative number of CH.sub.2 to CH.sub.3 groups increases. This is reflected in FIG. 9 by the CH.sub.2 peaks increasing in height and the CH.sub.3 peaks decreasing in height as the chain length increases.

[0113] FIG. 11 shows experimentally determined plots of absorbance against concentration of the respective group for the 2957 cm.sup.−1 CH.sub.3 peak, the 2853 cm.sup.−1 CH.sub.2 peak and the 2922 cm.sup.−1 CH.sub.2 peak. The plots demonstrate for all peaks reasonable linearity between absorbance and concentration (e.g. A(2957 cm.sup.−1)=0.0068[CH.sub.3]+0.030 and e.g. A(2853 cm.sup.−1)=0.0065[CH.sub.2]−0.127), and also reasonable sensitivity of absorbance to change in concentration.

[0114] Thus one option is to perform quantitative analysis of CH.sub.2 or CH.sub.3 group concentration based on infrared intensity measurements (a) filtered over a band corresponding to a respective peak of the dissolved species and (b) filtered over a band corresponding to a reference portion of the absorbance spectrum.

[0115] Another option is to use filters having pass bands at, for example, 2957 cm.sup.−1 (for CH.sub.3) and 2841 cm.sup.−1 (for CH.sub.2) to enable the CH.sub.2/CH.sub.3 ratio to be determined. This can useful for detecting contamination of oil-based drill fluids by crude oil during sampling.

[0116] In particular, crude oils show only modest variation in CH.sub.2/CH.sub.3 ratio. FIG. 12 shows mid-infrared absorbance spectra of a number of crude oils, with C.sub.7 and C.sub.10 alkane spectra also shown for reference. For North Sea crude the CH.sub.2/CH.sub.3 ratio is 3.48, for Cold Lake heavy oil is 3.65 and for Marmul crude it is 4.22. The CH.sub.2/CH.sub.3 ratios are thus within the range of n-alkanes C.sub.8-C.sub.11. FIG. 13 shows the mid-infrared absorbance spectra of the same crude oils superimposed with the spectra for three common base oils (HT 40N a, Escaid 110 and Clairsol 370). There is little discrimination between the spectra of the crude oils and the base oils. However, use of a synthetic base oil consisting of straight-chain alkanes enhances the contrast in the CH.sub.2/CH.sub.3 ratio. For example, Biobase 300 base oil available from M-I has a CH.sub.2/CH.sub.3 ratio of 4.13 and Sipdrill 2/0 base oil also from M-I has a CH.sub.2/CH.sub.3 ratio of 4.84. FIG. 14 shows again the mid-infrared absorbance spectra of the crude oils but now superimposed with the spectra for these two synthetic base oils.

[0117] Thus, using a reference filter and respective filters for CH.sub.2 and for CH.sub.3, allows an oil to be plotted on a graph of CH.sub.2/CH.sub.3 ratio against CH.sub.2 group concentration. FIG. 15 shows such a graph, with crude oils plotted as squares and base oils as triangles, and for reference the curve for n-alkanes also provided. Broadening of spectra for crude oils over base oils is one of the reasons why crude oils tend to exhibit higher a CH.sub.2/CH.sub.3 ratio for a given CH.sub.2 group concentration than base oils. Nonetheless, the two triangles at far right are the Biobase 300 and Sipdrill 2/0 synthetic base oils, demonstrating that such a plot provides a basis for discriminating between synthetic non-branched base oils and crude oils and thus detecting base oil contamination by crude oil.

Hydrate Inhibitor Concentration

[0118] A further possible use for the sensor of the type discussed above is to monitor hydrate inhibitor concentrations, for example in subsea locations, such as subsea pipelines.

[0119] Gas hydrates can form, particularly, in production pipelines. This is undesirable as the hydrates can agglomerate and block the flow and/or cause equipment damage. Two solutions are generally proposed. One is to add thermodynamic inhibitors, such as methanol, ethanol, monoethylene glycol or diethylene glycol, to the flow. These compounds may be recovered and recirculated. Although such thermodynamic inhibitors are cheap, they usually have to be added in large quantities in order to have a thermodynamic effect of lowering the hydrate formation temperature and/or delaying hydrate formation. The second is to add kinetic inhibitors, such as polyvinylpyrrolidone or polyvinylcaprolactam, to the flow. These work by slowing down the rate of hydrate nucleation and/or reducing hydrate agglomeration. They can be effective in lower doses, but are more expensive than most thermodynamic inhibitors.

[0120] With both types of inhibitor it is important to be able to measure the concentration of inhibitor in the liquid. Salt can be present in the liquid, sometimes in varying amounts. However, advantageously, the positions of mid-infrared absorption peaks of many inhibitors are not sensitive to salt concentration, making a mid-infrared sensor an attractive proposition for measuring inhibitor concentration.

[0121] FIG. 16 shows mid-infrared absorbance spectra of (a) monoethylene glycol in water, (b) methanol in water, and (c) ethanol in water, for different inhibitor concentrations from 0 to 100 vol %. FIG. 17 shows plots of absorbance against inhibitor concentration for (a) monoethylene glycol in water, (b) methanol in water, and (c) ethanol in water. For FIG. 17(a), the absorbances were measured using a band located on the 1084 cm.sup.−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. For FIG. 17(b), the absorbances were measured using a band located on the 1020 cm.sup.−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. For FIG. 17(c), the absorbances were measured using a band located on the 1045 cm.sup.−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. The plots of FIGS. 17(a) to (c) demonstrate good linearity between absorbance and concentration.

[0122] FIG. 18 shows mid-infrared absorbance spectra of (a) 50 vol % monoethylene glycol in water and in water saturated with NaCl, (b) 50 vol % methanol in water and in water saturated with NaCl, and (c) 50 vol % ethanol in water and in water saturated with NaCl. For monoethylene glycol, the 1084 cm.sup.−1 absorbance peak shifts in the presence of NaCl, but the position of an alternative 1040 cm.sup.−1 absorbance peak is static. This illustrates how a mid-infrared sensor in accordance with the present disclosure may be used to measure species, such as monoethylene glycol in the presence of NaCl. In particular, the mid-infrared sensor can be tuned, i.e., the filter can be tuned, to account for absorbance peak shifts in the presence of NaCl. For methanol, the position of the 1020 cm.sup.−1 absorbance peak is static, and for ethanol the position of the 1044 cm.sup.−1 absorbance peak is static.

[0123] FIG. 19 shows mid-infrared absorbance spectra at 50 vol % water of mixtures of monoethylene glycol and methanol, with the mixtures varying from 100% monoethylene glycol to 100% methanol. The right hand peak grows with increasing methanol, and the two left hand peaks grow with increasing monoethylene glycol. FIG. 20 shows plots of absorbance against concentration for respectively monoethylene glycol (diamonds) based on the leftmost peak and methanol (squares) based on the rightmost peak. Relative amounts of monoethylene glycol and methanol in a mixture can be determined from such plots.

[0124] FIG. 21 shows mid-infrared absorbance spectra of polyvinylpyrrolidone in water, for different inhibitor concentrations from 0 to 5 wt %, and FIG. 22 shows a plot of absorbance against inhibitor concentration for polyvinylpyrrolidone in water, using a band located on the 1295 cm.sup.−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. The plot of FIG. 22 demonstrates good linearity between absorbance and concentration. FIG. 23 shows mid-infrared absorbance spectra of 5 wt % polyvinylpyrrolidone in water and in water saturated with NaCl, the position of the 1295 cm.sup.−1 absorbance peak being static. Thus as with the other species, such an inhibitor can be measured in the presence of salt as absorption can be differentiated and/or the sensor can be tuned for movement of the peaks in the presence of salt.

Mineral Acid Concentration

[0125] Another possible use for the sensor of the type discussed above is to monitor mineral acid concentrations. For example, HCl is extensively pumped in coiled tubing for stimulation of carbonate formations. The high mineral acid concentration typically used in such operations often makes pH measurements unsuitable. However, the sensor can be deployed to enable HCl concentration to be monitored to evaluate acidisation efficiency. Again, the ability of the sensor to operate under a full range of downhole temperatures is advantageous.

[0126] FIG. 24 shows mid-infrared absorbance spectra of HCl in water, for different HCl concentrations from 0 to 40 wt %, and FIG. 25 shows a plot of absorbance against HCl concentration for HCl in water, using a band located on the 1050 cm.sup.−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. The plot of FIG. 25 demonstrates good linearity between absorbance and concentration. NaCl is not a factor with respect to HCl use in the petrochemical industry, however, CaCl will be a return product in downhole HCl applications

[0127] The 1050 cm.sup.−1 absorbance peak is apparently due to dissociated HCl, the peak only emerging as the HCl concentration rises. Further evidence that the peak is due to dissociated HCl comes from measurements of DCl in D.sub.2O. FIG. 26 shows mid-infrared absorbance spectra of DCl in D.sub.2O, for different DCl concentrations from 0 to 35 wt %. As expected, all the peaks shown in FIG. 24 are shifted in FIG. 26 to lower wavenumbers by approximately 1/√2. For completeness, FIG. 27 shows a plot of absorbance against DCl concentration for DCl in D.sub.2O, using a band located on the 850 cm.sup.−1 absorbance peak (shifted from 1050 cm.sup.−1 in FIG. 24) and a band corresponding to a reference portion of the absorbance spectrum.

[0128] The 1050 cm.sup.−1 absorbance peak is also exhibited by HBr and HI, as illustrated by FIG. 28 which shows mid-infrared absorbance spectra of 4.2 M HCl in water, 4.7 M HBr in water and 4.5 M HI in water, suggesting that the peak is caused by a hydrated proton. FIG. 29 shows the corresponding plots of absorbance against acid concentration using a band located on the 1050 cm.sup.−1 absorbance peak.

Carbon Dioxide Concentration

[0129] The analysis of fluid samples from hydrocarbon wells for the determination of phase behaviour and chemical composition is a critical step in the evaluation of the producibility and economic value of the hydrocarbon reserves. An important factor in determining the economic value of gas and liquid hydrocarbon reserves is their chemical composition, particularly the concentration of gaseous components, such as carbon dioxide. Similarly, the monitoring of fluid composition during production operations can have an important bearing on reservoir management decisions, such as ceasing production from certain zones or applying chemical treatments to producing wells.

[0130] A mid-infrared sensor, of the type discussed above, in accordance with an embodiment of the present disclosure, may be used to monitor CO.sub.2 concentrations downhole. In particular, in some embodiments of the present disclosure, the sensor may comprise three narrow bandpass filters 5 corresponding to respective absorbance peaks of water, oil and CO.sub.2, and a second narrow bandpass filter 5′ for a reference portion of the absorbance spectrum. Such an arrangement allows the CO.sub.2 concentration to be determined when the window 4 is wetted by a liquid water phase, a liquid oil phase, a mixture of liquid water and liquid oil phases, or when the window is dry.

[0131] For example, FIG. 30(a) shows an absorbance spectrum for the case where the window 4 is wetted by a water phase. The spectrum is characterised by high absorption by water at 3.00 μm, almost no absorption by oil at 3.45 μm. The CO.sub.2 concentration is proportional to the net CO.sub.2 absorption, which is the difference between the CO.sub.2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO.sub.2 concentration in the water phase to be determined from CO.sub.2 absorption can be obtained from an experimental plot of CO.sub.2 absorbance against dissolved CO.sub.2 concentration in water, such as shown in FIG. 30(b).

[0132] Similarly, FIG. 31(a) shows an absorbance spectrum for the case where the window 4 is wetted by an oil phase. The spectrum is characterised by high absorption by oil at 3.45 μm almost no absorption by water at 3.00 μm. Again, the CO.sub.2 concentration is proportional to the net CO.sub.2 absorption, which is the difference between the CO.sub.2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO.sub.2 concentration in the oil phase to be determined from CO.sub.2 absorption can be obtained from an experimental plot of CO.sub.2 absorbance against dissolved CO.sub.2 concentration in oil, such as shown in FIG. 31(b).

[0133] Next, FIG. 32 shows an absorbance spectrum for the case where the window 4 is wetted by a mixture of water and oil phases. The spectrum is characterised by absorption by water at 3.00 μm and by oil at 3.45 μm. Again the CO.sub.2 concentration is proportional to the net CO.sub.2 absorption, which is the difference between the CO.sub.2 channel at 4.27 μm and the reference channel at 4.00 μm. However, the proportionality constant is slightly different for water and for oil because their refractive indices, and thus their depths of investigation, are different. Specifically, oil has higher refractive index than water, thus its depth of investigation is deeper and potentially more CO.sub.2 is sensed by the sensor in oil than in water. Thus, when the window is wetted by a mixture of both water and oil phase, the mixture proportionality constant is between those of water and oil, but can be calculated from therefrom. For example, In some embodiments of the present disclosure, a “lever rule” may be used, whereby if the water peak height is X% of its full height and the oil peak height is (100−X)% of its full height, the mixture proportionality constant is the sum of X% of the water proportionality constant and (100−X)% of the oil proportionality constant. More elaborate schemes can be used, in other embodiments, but the simple “lever rule” approach works reasonably well because the difference between the water and oil proportionality constants is in any event not great.

[0134] Under some circumstances, the sensor window 5 may be dry. The spectrum is characterised by almost no absorption by water at 3.00 μm or by oil at 3.45 μm. CO.sub.2 concentration is proportional to the net CO.sub.2 absorption, which is the difference between the CO.sub.2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO.sub.2 concentration in the gas phase to be determined from CO.sub.2 absorption can, in accordance with an embodiment of the present disclosure, be obtained from an experimental plot of CO.sub.2 absorbance against CO.sub.2 concentration in gas phase, such as shown in FIG. 33.

[0135] Monitoring of CO.sub.2 concentration can be particularly useful when performed in combination with monitoring of mineral acid concentrations. In particular, a mineral acid sensor can provide a measure of how much acid is being deployed to stimulate a carbonate formation, and the CO.sub.2 sensor, by measuring the amount of CO.sub.2 produced, can provide a measure of the effectiveness of that acid deployment.

Heater

[0136] As mentioned above, the sensor of FIG. 1 comprises a heater 8 which is operable to locally heat the window 4, thereby cleaning the surface of the window in contact with the fluid. Use of localized heat on the active surface of the window has been found to provide for effective cleaning of the surface.

[0137] In some embodiments of the present disclosure, the window 4 may be formed, for example, of diamond (e.g. by chemical vapour deposition or the like). In some embodiments of the present disclosure, a central (typically undoped) area of the window can be mid-infrared transmissive, while an annular encircling area of the window can be made semiconductive, e.g. by boron doping that part of the window. In some embodiments of the present disclosure, the heater 8 may comprise an electrical power source that is configured to send a current through the window to induce resistive heating of the encircling area. The central area of the window may then heated by thermal conduction from the encircling area. Boron-doping of diamond components is discussed in U.S. Pat. No. 7,407,566, which is incorporated by reference herein for all purposes.

[0138] In some embodiments, the heater 8 is configured to heat the window to at least about 400° C. This is higher than the 374° C. super-critical point for water, super-critical water being a good cleaner and oxidiser. In some embodiments of the present disclosure, the window is not maintained at a high temperature for a long time period. In particular, in some embodiments, the active surface may be held at the elevated temperature for less than about a microsecond. Such short durations at peak temperature may be enough for cleaning purposes, with longer periods requiring more power and increasing the risk of overheating of other parts of the sensor. In some embodiments of the present disclosure, doping of the sapphire/diamond window may be configured to provide temperature increases at certain locations on the sensing window, distributed temperature increases across the window, thermal conductivity across the active surface and/or the like. In some embodiments, heating may be coordinated with sensor measurements so that the heating may produce a thermal mixing of the fluid in front of the sensor window.

[0139] All references referred to above are hereby incorporated by reference.

[0140] The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the scope of the present disclosure, and that they may make various changes, substitutions and alterations herein without departing from such scope.