Electrochemical sensor system

• US 9,523,667 B2
• Filed: 08/13/2012
• Issued: 12/20/2016
• Est. Priority Date: 08/15/2011
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: Lafitte, Valerie, Tustin, Gary John
• Primary Examiner(s): Van, Luan
• Assistant Examiner(s): Rosenwald, Steven E
• Application Number:
  US13/584,587
• Publication Number:
  US 20130062222A1
• Time in Patent Office: 1,590 Days
• Field of Search: 205/786.5, 205/793, 205/775
• US Class Current: 1/1
• CPC Class Codes: E21B 49/0875 determining specific fluid parameters
• CPC Class Codes: G01N 27/48 using polarography, i.e. measuring changes in current under a slowly-varying voltage
• CPC Class Codes: G01N 33/2823 Raw oil, drilling fluid or polyphasic mixtures

Abstract

An electrochemical sensor measuring concentration of an analyte in a test fluid at 50° C. or above by voltammetry uses electrodes in contact with an electrolyte containing the analyte and a redox-active species electrochemically convertible between reduced and oxidised forms. At least one form of the redox active species is present within surfactant micelles. The surfactant micelles enhance thermal stability of the redox active species and may also solubilise a species with poor water solubility, such as t-butylferrocene. A downhole tool incorporating such a sensor comprises a barrier, permeable to the analyte, to separate the electrolyte from subterranean reservoir fluid, so that the sensor directly measures analyte which has passed through the barrier and thereby indirectly measures analyte in the test fluid.

Claims

1. A method of measuring concentration of hydrogen sulfide or thiol analyte in a subterranean test fluid at a temperature of 50°

to 125°

C. in a well comprising;

providing a plurality of electrodes in contact with an electrolyte solution containing a redox-active species electrochemically convertible between reduced and oxidized forms, wherein the electrolyte solution contains surfactant and at least one said form of the redox active species is present within surfactant micelles; and

bringing the electrolyte and a test fluid containing the analyte into contact with opposite sides of a membrane, which is permeable to the hydrogen sulfide or thiol analyte so that analyte can migrate through the membrane into the electrolyte solution; and

applying potential to the electrodes and observing current flow as voltage is varied;

wherein the redox-active species comprises ferrocene which is substituted with at least one substituent group which is an alkyl group of 1 to 6 carbon atoms or an alkenyl group of 2 to 6 carbon atoms such that the water solubility of the substituted ferrocene is less than the water solubility of unsubstituted ferrocene; and

wherein the substituted ferrocene is solubilized by the surfactant micelles.

2. A method according to claim 1 wherein application of potential and observation of current obtains a voltammetric response.

3. A method according to claim 1 which comprises bringing the test fluid into contact with a barrier which separates the test fluid from said electrolyte but which is permeable to the hydrogen sulfide or thiol so that hydrogen sulfide or thiol can migrate into said electrolyte through the barrier.

4. A method according to claim 1 wherein the surfactant is cationic.

5. A method according to claim 1 wherein the surfactant is anionic.

6. A method according to claim 1 wherein the redox-active species is 1,1-diethyl ferrocene.

7. A method according to claim 1 wherein the redox-active species is t-butyl ferrocene.

8. A method according to claim 1 wherein the redox-active species is vinyl ferrocene.