WO1994028399A1 - Sensors for sulfur activity measurements - Google Patents
Sensors for sulfur activity measurements Download PDFInfo
- Publication number
- WO1994028399A1 WO1994028399A1 PCT/US1994/005757 US9405757W WO9428399A1 WO 1994028399 A1 WO1994028399 A1 WO 1994028399A1 US 9405757 W US9405757 W US 9405757W WO 9428399 A1 WO9428399 A1 WO 9428399A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfide
- sulfur
- sensor
- activity
- sulfur activity
- Prior art date
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 45
- 239000011593 sulfur Substances 0.000 title claims abstract description 45
- 230000000694 effects Effects 0.000 title claims abstract description 35
- 238000005259 measurement Methods 0.000 title description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims abstract description 13
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical group [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 5
- 230000003628 erosive effect Effects 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 150000004763 sulfides Chemical class 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/287—Sulfur content
Definitions
- the present invention relates to measuring the thermodynamic sulfur activity in a process environment.
- the present invention includes a method and a sensor to measure sulfur activity.
- thermodynamic activity of sulfur which is established in the environment by the interplay of the various sulfur containing corrosive species.
- Sulfur activity is a well known measure of the available sulfur for reaction (see e.g., "An Analysis of the Phase Equilibria in the Fe-FeS System", Metallurgical Transactions B, p. 37-41, Vol. 6B, March 1975).
- temperature ranges 150°F to 1000 ⁇ F The thermodynamic activity of sulfur can be used as a generalized index of corrosivity. Thus, if the sulfur activity can be directly measured by means of a sensor, this will provide a determination of corrosivity prediction.
- the present invention includes a method and a device to determine the sulfur activity in a given environment (such as a feedstream) . This activity can be related to the sulfur concentration in the environment.
- the sensor includes several elements: a non-stoichiometric sulfide, M ⁇ _ ⁇ S, whose conductivity varies with sulfur activity where the maximum value of x is between .002 and 0.5; electrodes attached to the sulfide; and a means for measuring the conductivity of said sulfide and correlating the electrical conductivity with the sulfur activity.
- the sulfide is iron sulfide (pyrrhotite) or cuprous sulfide.
- the sensor is placed in an environment whose sulfur activity is to be determined.
- the conductivity and hence, resistivity of the sulfide is measured.
- the corresponding sulfur activity and sulfur concentration may then be determined from a calibration curve of the conductivity (or resistivity) vs. sulfur activity.
- Figure 1 shows the resistivity (inverse of conductivity) of a cuprous sulfide foil as a function of the sulfur activity at 1000 ⁇ F.
- the sulfur activity was established using equilibrated H2S/H2 mixtures.
- Figure 2 shows the resistivity (inverse of conductivity) of an iron sulfide foil as a function of the sulfur activity in the H S/H2 mixture at 1000°F.
- Figure 3 shows a schematic diagram of an embodiment the sensor of the present invention.
- the present invention includes a method and a device to determine the sulfur activity in a given environment (such as a feed stream) at a temperature which will be limited to below 1000°F for such applications.
- One of the elements of the device is a non-stoichio etric metal sulfide M ⁇ - ⁇ S whose metal to sulfur ratio ( ⁇ -x) varies over a wide range and whose conductivity varies with sulfur activity.
- the measurement of conductivity variation is made possible by the rapid diffusion of metal ions in these non-stoichiometric sulfides.
- x S is defined by the deviation, x of the M/S ratio from the stoichiometric constant, a .
- a is defined as the metal to sulfur ratio in the binary sulfide when there is no deviation from stoichiometry.
- the maximum value of x (xmax) is in the range 0.002 ⁇ x ma ⁇ 0.5.
- x ma ⁇ is in the range 0.02 ⁇ x m a ⁇ 0.5.
- the larger non-stoichiometry range allows rapid atomic diffusion in the temperature range (below 1000°F) where sensors are used.
- the non-stoichiometry of the sulfides is due to the metal deficiency on the cation lattice while the anion lattice is nearly perfect.
- the sensor also includes electrodes attached to the sulfide and a means for measuring the electrical conductivity of the said sulfide and correlating the conductivity with the sulfur activity.
- the sensor includes a non-stoichiometric sulfide which in general is a p-type or n-type semi-conductor.
- a non-stoichiometric sulfide which in general is a p-type or n-type semi-conductor.
- the presence of metal vacancies balanced by electron holes provides semi conduction in the former case while metal interstitials balanced by excess electrons causes semi conduction in the latter case.
- the measured total conductivity is essentially equal to the p-type or the n-type conductivity which is proportional to the metal deficit or metal excess of the sulfide, which in turn is directly related to the sulfur chemical potential or activity of the environment.
- Metal sulfides useful in the present invention include Cu2- ⁇ S, Fei- x S, Co ⁇ _ ⁇ S, Ni3S2+ ⁇ .
- One method of practicing this invention is to prepare thin self supporting foils of the non-stoichiometric sulfide sensor and use four probe d.c. techniques to measure its electrical conductivity. This can be done by first starting with a metal foil to which inert metal electrodes are spot welded. The foil/electrode assembly is then exposed to a controlled sulfur environment whereby the metal foil is converted to the non-stoichiometric sulfide sensor element. The sensor is then ready for placement in the process stream. The steady state conductivity of the foil provides a measure of the sulfur activity of the stream.
- the sulfur activity-conductivity relationship for the sulfur sensors may be determined by using iron foils and copper foils in H2S/H2 mixtures of known sulfur activity.
- the foils convert to the corresponding sulfides.
- Figures 1 and 2 show the resistivity (inverse of conductivity) of cuprous sulfide and iron sulfide foils respectively as a function of the sulfur activity in the H2S/H mixture at 1000°F. These figures serve as a calibration plot of conductivity vs. sulfur activity. Shown in the inset are relaxation curves of the variation of resistivity with time when the environment is changed from one sulfur content to another. This provides a measure of the response time of the sensor at 1000"F.
- the sensor may be made more durable by replacing the sulfide foils with thin sulfide films deposited on a non-conductive ceramic substrate (see Figure 3). This will provide for enhanced mechanical integrity as well as faster response times.
- a suitable substrate (1) could be a ceramic wafer with conductive electrodes (2) formed by thin or thick film techniques which are well known in the art.
- One method of practicing this invention is to deposit a thin film of the metal by sputtering or evaporation and subsequently converting the metal film into a sulfide (3).
- Another technique could be to deposit the metal sulfide layer in a single step by reactive sputter deposition. Such thin film deposition techniques are also well known in the art.
- the sensor of the present invention may include an erosion resistant porous ceramic layer (4) between the sensor and the process stream.
- Such a membrane layer could be formed by solgel techniques, for example.
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
A method and a sensor to measure the sulfur activity in sulfur-containing environments are disclosed. The active component is a non-stoichiometric metal sulfide foil or film (3). In the case of a thin sulfide film, a ceramic substrate (1) is employed for improved mechanical rigidity. The electrical conductivity of the sulfide is related to the sulfur activity of the process stream to which it is exposed.
Description
SENSORS FOR SULFUR ACTIVITY MEASUREMENTS
BACKGROUND OF THE INVENTION
The present invention relates to measuring the thermodynamic sulfur activity in a process environment. In particular, the present invention includes a method and a sensor to measure sulfur activity.
In many processes, for example in the refining of crudes or in sour gas production wells, there is a significant need to measure the thermodynamic activity of sulfur which is established in the environment by the interplay of the various sulfur containing corrosive species. Sulfur activity is a well known measure of the available sulfur for reaction (see e.g., "An Analysis of the Phase Equilibria in the Fe-FeS System", Metallurgical Transactions B, p. 37-41, Vol. 6B, March 1975). To provide operational flexibility in these environments, it is of great interest to predict the rates of corrosion. Typically, these environments exhibit temperature ranges 150°F to 1000βF. The thermodynamic activity of sulfur can be used as a generalized index of corrosivity. Thus, if the sulfur activity can be directly measured by means of a sensor, this will provide a determination of corrosivity prediction.
SUMMARY OF THE INVENTION
The present invention includes a method and a device to determine the sulfur activity in a given environment (such as a feedstream) . This activity can be related to the sulfur concentration in the environment.
The sensor includes several elements: a non-stoichiometric sulfide, Mα_χS, whose conductivity varies with sulfur activity where the maximum value of x is between .002 and 0.5; electrodes attached to the sulfide; and a means for measuring the conductivity of said sulfide and correlating the electrical conductivity with the sulfur activity.
In a preferred embodiment, the sulfide is iron sulfide (pyrrhotite) or cuprous sulfide.
The sensor is placed in an environment whose sulfur activity is to be determined. The conductivity and hence, resistivity of the sulfide is measured. The corresponding sulfur activity and sulfur concentration may then be determined from a calibration curve of the conductivity (or resistivity) vs. sulfur activity.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the resistivity (inverse of conductivity) of a cuprous sulfide foil as a function of the sulfur activity at 1000βF. The sulfur activity was established using equilibrated H2S/H2 mixtures.
Figure 2 shows the resistivity (inverse of conductivity) of an iron sulfide foil as a function of the sulfur activity in the H S/H2 mixture at 1000°F.
Figure 3 shows a schematic diagram of an embodiment the sensor of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention includes a method and a device to determine the sulfur activity in a given environment (such as a feed stream) at a temperature which will be limited to below 1000°F for such applications. One of the elements of the device is a non-stoichio etric metal sulfide Mα-χS whose metal to sulfur ratio (α-x) varies over a wide range and whose conductivity varies with sulfur activity. The measurement of conductivity variation is made possible by the rapid diffusion of metal ions in these non-stoichiometric sulfides. The non-stoichio etry of the binary sulfide Mα.xS is defined by the deviation, x of the M/S ratio from the stoichiometric constant, a . a is defined as the metal to sulfur ratio in the binary sulfide when there is no deviation from stoichiometry. For the sulfides of the present invention, the maximum value of x (xmax) is in the range 0.002
<xmaχ<0.5. In a preferred embodiment, xmaχ is in the range 0.02<xmaχ<0.5. Examples of sulfides of our invention are Cu2-χS (xmax=0.23) , Feι_xS (xmax=0.25). The larger non-stoichiometry range allows rapid atomic diffusion in the temperature range (below 1000°F) where sensors are used. The non-stoichiometry of the sulfides is due to the metal deficiency on the cation lattice while the anion lattice is nearly perfect. The sensor also includes electrodes attached to the sulfide and a means for measuring the electrical conductivity of the said sulfide and correlating the conductivity with the sulfur activity.
The sensor includes a non-stoichiometric sulfide which in general is a p-type or n-type semi-conductor. The presence of metal vacancies balanced by electron holes provides semi conduction in the former case while metal interstitials balanced by excess electrons causes semi conduction in the latter case. The measured total conductivity is essentially equal to the p-type or the n-type conductivity which is proportional to the metal deficit or metal excess of the sulfide, which in turn is directly related to the sulfur chemical potential or activity of the environment. Metal sulfides useful in the present invention include Cu2-χS, Fei-xS, Coι_χS, Ni3S2+χ.
One method of practicing this invention is to prepare thin self supporting foils of the non-stoichiometric sulfide sensor and use four probe d.c. techniques to measure its electrical conductivity. This can be done by first starting with a metal foil to which inert metal electrodes are spot welded. The foil/electrode assembly is then exposed to a controlled sulfur environment whereby the metal foil is converted to the non-stoichiometric sulfide sensor element. The sensor is then ready for placement in the process stream. The steady state conductivity of the foil provides a measure of the sulfur activity of the stream.
The sulfur activity-conductivity relationship for the sulfur sensors may be determined by using iron foils and copper foils in H2S/H2 mixtures of known sulfur activity. The foils convert to the corresponding sulfides. Figures 1 and 2 show the resistivity (inverse of conductivity) of cuprous sulfide and iron sulfide foils respectively as a function of the sulfur
activity in the H2S/H mixture at 1000°F. These figures serve as a calibration plot of conductivity vs. sulfur activity. Shown in the inset are relaxation curves of the variation of resistivity with time when the environment is changed from one sulfur content to another. This provides a measure of the response time of the sensor at 1000"F.
The sensor may be made more durable by replacing the sulfide foils with thin sulfide films deposited on a non-conductive ceramic substrate (see Figure 3). This will provide for enhanced mechanical integrity as well as faster response times. A suitable substrate (1) could be a ceramic wafer with conductive electrodes (2) formed by thin or thick film techniques which are well known in the art. One method of practicing this invention is to deposit a thin film of the metal by sputtering or evaporation and subsequently converting the metal film into a sulfide (3). Another technique could be to deposit the metal sulfide layer in a single step by reactive sputter deposition. Such thin film deposition techniques are also well known in the art.
In many process streams, erosive damage of sensor components can occur because of particulate and velocity effects. The sensor of the present invention may include an erosion resistant porous ceramic layer (4) between the sensor and the process stream. Such a membrane layer could be formed by solgel techniques, for example.
Claims
1. A method to determine the sulfur activity in a sulfur containing environment having a temperature less than 1000°F comprising:
(a) contacting said environment with a non-stoichiometric metal sulfide MQT-XS, whose electrical conductivity varies with the sulfur activity, where the maximum value of x is between 0.002 and 0.5;
(b) measuring the electrical conductivity of said sulfide; and
(c) correlating said conductivity with the sulfur activity in said environment.
2. The method of claim 1 wherein said sulfide is iron sulfide or copper sulfide.
3. A sensor for determining the sulfur activity in an environment comprising:
(a) non-stoichiometric metal sulfide, Mα.χS, whose electrical conductivity varies with sulfur activity, where the maximum value of x is between 0.002 and 0.5;
(b) electrodes attached to said sulfide; and
(c) means for measuring the electrical conductivity of said sulfide and correlating said conductivity with the sulfur activity.
4. The sensor of claim 3 wherein said sulfide is iron sulfide or copper sulfide.
5. The sensor of claim 3 wherein said sulfide is a thin self supporting foil.
6. The sensor of claim 3 wherein said sulfide is a thin film deposited on a substrate.
7. The sensor of claim 6 wherein said substrate is a ceramic material.
8. The sensor of claim 6 further comprising a porous, corrosion and erosion resistant layer between said sulfide and said environment.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002163208A CA2163208C (en) | 1993-05-20 | 1994-05-20 | Sensors for sulfur activity measurements |
| JP50085895A JP3423953B2 (en) | 1993-05-20 | 1994-05-20 | Sulfur activity measurement method and sensor |
| EP94920680A EP0700517B1 (en) | 1993-05-20 | 1994-05-20 | Sensors for sulfur activity measurements |
| DE69422515T DE69422515T2 (en) | 1993-05-20 | 1994-05-20 | SENSORS FOR MEASURING SULFUR ACTIVITY |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6426293A | 1993-05-20 | 1993-05-20 | |
| US08/245,341 | 1994-05-18 | ||
| US08/064,262 | 1994-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994028399A1 true WO1994028399A1 (en) | 1994-12-08 |
Family
ID=22054688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1994/005757 WO1994028399A1 (en) | 1993-05-20 | 1994-05-20 | Sensors for sulfur activity measurements |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5464523A (en) |
| WO (1) | WO1994028399A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025413A1 (en) * | 2004-08-30 | 2006-03-09 | Japan Science And Technology Agency | Nonvolatile phase change magnetic material, manufacturing method thereof, and nonvolatile phase change magnetic memory using the same |
| KR20150086750A (en) * | 2014-01-20 | 2015-07-29 | 한국전자통신연구원 | Chalcogen gas monitoring device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3437446A (en) * | 1965-10-23 | 1969-04-08 | Abcor Inc | Apparatus for and method of detecting sulfur-containing compounds |
| US3558280A (en) * | 1968-11-05 | 1971-01-26 | Westinghouse Electric Corp | Solid state oxygen gauge |
| US4406754A (en) * | 1980-03-28 | 1983-09-27 | Kabushiki Kaisha Kobe Seiko Sho | Method and probe for the rapid determination of sulfur level |
| US4507643A (en) * | 1982-08-06 | 1985-03-26 | Naomasa Sunano | Gas sensor with improved perovskite type material |
| US4885929A (en) * | 1987-10-08 | 1989-12-12 | New Cosmos Electric Co. Ltd. | Ozone gas sensor and ozone gas detecting device having ozone gas sensor |
| US5082789A (en) * | 1988-08-23 | 1992-01-21 | Simon Fraser University | Bismuth molybdate gas sensor |
-
1994
- 1994-05-18 US US08/245,341 patent/US5464523A/en not_active Expired - Lifetime
- 1994-05-20 WO PCT/US1994/005757 patent/WO1994028399A1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3437446A (en) * | 1965-10-23 | 1969-04-08 | Abcor Inc | Apparatus for and method of detecting sulfur-containing compounds |
| US3558280A (en) * | 1968-11-05 | 1971-01-26 | Westinghouse Electric Corp | Solid state oxygen gauge |
| US4406754A (en) * | 1980-03-28 | 1983-09-27 | Kabushiki Kaisha Kobe Seiko Sho | Method and probe for the rapid determination of sulfur level |
| US4507643A (en) * | 1982-08-06 | 1985-03-26 | Naomasa Sunano | Gas sensor with improved perovskite type material |
| US4885929A (en) * | 1987-10-08 | 1989-12-12 | New Cosmos Electric Co. Ltd. | Ozone gas sensor and ozone gas detecting device having ozone gas sensor |
| US5082789A (en) * | 1988-08-23 | 1992-01-21 | Simon Fraser University | Bismuth molybdate gas sensor |
Non-Patent Citations (2)
| Title |
|---|
| NODDACK et al., "The Electrochemical Series of the Sulfides", Z. Electrochem., Vol. 59, (1955), pages 752-755. * |
| See also references of EP0700517A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US5464523A (en) | 1995-11-07 |
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