Source: https://patents.justia.com/patent/10539500
Timestamp: 2020-02-28 13:27:19
Document Index: 791735369

Matched Legal Cases: ['art 1', 'Application No. 1416268', 'Application No. 1416268', 'Application No. 1416256', 'Application No. 1416257', 'Application No. 1416260', 'Application No. 1416264', 'Application No. 1416265', 'Application No. 1416265', 'Application No. 201580061274']

US Patent for Active surface cleaning for a sensor Patent (Patent # 10,539,500 issued January 21, 2020) - Justia Patents Search
Justia Patents With Source And DetectorUS Patent for Active surface cleaning for a sensor Patent (Patent # 10,539,500)
Sep 9, 2015 - SCHLUMBERGER TECHNOLOGY CORPORATION
FIGS. 1A and 1B show 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;
FIGS. 4A and 4B show 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;
FIGS. 5A to 5B show (a) a reference intensity spectrum I0 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;
FIGS. 16A to 16C show 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 %;
FIGS. 17A to 17C show plots of absorbance against inhibitor concentration for (a) monoethylene glycol in water, (b) methanol in water, and (c) ethanol in water;
FIGS. 18A to 18C show 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;
FIGS. 30A and 30B show (a) a mid-infrared absorbance spectrum for a water phase and CO2, and (b) a corresponding plot of absorbance against CO2 concentration for CO2 in H2O;
FIGS. 31A and 31B show (a) a mid-infrared absorbance spectrum for an oil phase and CO2, and (b) a corresponding plot of absorbance against CO2 concentration for CO2 in oil;
FIG. 32A shows a mid-infrared absorbance spectrum for a water phase, an oil phase and CO2; and
FIG. 32B shows a plot of absorbance against CO2 concentration for CO2 in gas phase.
FIG. 1A 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.
FIG. 1B 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.
The optical thickness nd cos θ of the substrate S, where n is the refractive index of the substrate, is equal to an integer number of half wavelengths λm, where λm 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 λm through the filter is thus mλm/2=nd cos θ, where m is an integer.
d ⁢ ⁢ λ m dT ⁢ ❘ s = 2 ⁢ n L ⁢ d L ⁡ ( C L + dn L n L ⁢ dT ) + 2 ⁢ n H ⁢ d H ⁡ ( C H + dn H n H ⁢ dT )
d ⁢ ⁢ λ m dT ⁢ ❘ c = 2 ⁢ yn L ⁢ d L ⁡ ( C L + dn L n L ⁢ dT )
d ⁢ ⁢ λ m dT ⁢ ❘ T = 2 ⁢ ( 1 + y ) ⁢ n L ⁢ d L ⁡ ( C L + dn L n L ⁢ dT ) + 2 ⁢ n H ⁢ d H ⁡ ( C H + dn H n H ⁢ dT ) or d ⁢ ⁢ λ m ⁢ λ m ⁢ dT ⁢ ❘ T = ( 1 + y ) ⁢ ( C L + dn L n L ⁢ dT ) + ( C H + dn H n H ⁢ dT )
dn H n L ⁢ dT = - ( 1 + y ) ⁢ dn L n L ⁢ dT
noting that Ci is considerably smaller than dni/nidT 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 nL=2.43, nH=6.10, dnL/dT=6.3×10−5 K−1 and dnH/dT=−2.1×10−3 K−1 for λm=3.4 μm, the expression is satisfied with y=13.3, i.e., approximately 13 half wavelength cavity layers are required to achieve the condition dλm/dT|T=0.
There is considerable variation in the values of the material properties (nH, dnH/dT, CH, etc.) that appear in for thin films in a multilayer structure and therefore in the predicted value of dλm/λmdT or the value of y required to achieve the condition dλm/λmdT=0. The uncertainty is particularly severe for the value of dnH/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 λm=5 μm has been reported to be −1.5×10−3 K−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), −2.7×10−3 K−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 −2.8×10−3 K−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.
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 dλm/dT=0, a more useful approach is to determine the experimental value of dλm/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 dλm/λmdT 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 dλm/λmdT 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 λm<5 μm, the condition dλm/λmdT=0 is met by a 4:4:4 (i.e., 3 full wavelength or 6 half wavelength cavities (y=6)) filter, while for λm>5 μm a 6:4:6 (y=8) filter is required.
FIGS. 4A and 4B show 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 dλm/dT for the λm=4.26 μm (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 dλm/dT for the λm=12.1 μm (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.
The Beer-Lambert law applied to the sensor of FIGS. 1A and 1B provides that:
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 I0 is a reference intensity spectrum. For example, FIGS. 5A-5C show (a) a reference intensity spectrum I0 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.
FIGS. 16A-16C show 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 %. FIGS. 17A-17C show 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−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. For FIG. 17B, the absorbances were measured using a band located on the 1020 cm−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. For FIG. 17C, the absorbances were measured using a band located on the 1045 cm−1 absorbance peak and a band corresponding to a reference portion of the absorbance spectrum. The plots of FIGS. 17A to 17C demonstrate good linearity between absorbance and concentration.
FIGS. 18A to 18C show 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−1 absorbance peak shifts in the presence of NaCl, but the position of an alternative 1040 cm−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−1 absorbance peak is static, and for ethanol the position of the 1044 cm−1 absorbance peak is static.
For example, FIG. 30A 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 CO2 concentration is proportional to the net CO2 absorption, which is the difference between the CO2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO2 concentration in the water phase to be determined from CO2 absorption can be obtained from an experimental plot of CO2 absorbance against dissolved CO2 concentration in water, such as shown in FIG. 30B.
Similarly, FIG. 31A 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 CO2 concentration is proportional to the net CO2 absorption, which is the difference between the CO2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO2 concentration in the oil phase to be determined from CO2 absorption can be obtained from an experimental plot of CO2 absorbance against dissolved CO2 concentration in oil, such as shown in FIG. 31B.
Next, FIG. 32A 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 CO2 concentration is proportional to the net CO2 absorption, which is the difference between the CO2 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 CO2 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.
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. CO2 concentration is proportional to the net CO2 absorption, which is the difference between the CO2 channel at 4.27 μm and the reference channel at 4.00 μm. The proportionality constant allowing CO2 concentration in the gas phase to be determined from CO2 absorption can, in accordance with an embodiment of the present disclosure, be obtained from an experimental plot of CO2 absorbance against CO2 concentration in gas phase, such as shown in FIG. 32B.
As mentioned above, the sensor of FIGS. 1A and 1B 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.
11. The sensor according to claim 1 which is adapted for monitoring CO2 concentration in the fluid, the sensor having three first narrow bandpass filters corresponding to respective absorbance peaks of water, oil and CO2,
12. A well tool including the sensor of claim 1.
13. 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.
14. The sensor according to claim 13, wherein the high refractive index layers are formed of one or more of PbTe, PbSe, PbS, or Ge.
15. The sensor according to claim 13, wherein the low refractive index layers are formed of one or more of ZnS or ZnSe.
16. The sensor according to claim 13, wherein each layer in the stacks of alternating layers of high and low refractive index has an optical thickness of about one quarter wavelength.
17. The sensor according to claim 13, 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.
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Patent number: 10539500
Patent Publication Number: 20170241899
International Classification: B08B 7/00 (20060101); G02B 1/02 (20060101); G01N 21/15 (20060101); G01N 21/35 (20140101); G01N 21/3577 (20140101); G02B 27/00 (20060101); G01N 21/31 (20060101); G01N 21/552 (20140101); G01N 33/28 (20060101); G01N 21/3504 (20140101); G02B 5/28 (20060101);