Systems and methods for detection of mercury in hydrocarbon-containing fluids using optical analysis of slug flow

• US 10,359,412 B2
• Filed: 09/01/2016
• Issued: 07/23/2019
• Est. Priority Date: 09/01/2016
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: van Hal, Ronald E. G., Sieben, Vincent, Floquet, Cedric, Lee, Victoria
• Primary Examiner(s): Jarrett, Lore R
• Application Number:
  US15/254,925
• Publication Number:
  US 20180059088A1
• Time in Patent Office: 1,055 Days
• CPC Class Codes: G01N 1/00 Sampling; Preparing specimens for investigation
• CPC Class Codes: G01N 21/00 Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light G01N3/00 - G01N19/00 take precedence
• CPC Class Codes: G01N 21/554 detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
• CPC Class Codes: G01N 21/77 by observing the effect on a chemical indicator
• CPC Class Codes: G01N 21/85 Investigating moving fluids or granular solids
• CPC Class Codes: G01N 33/2858 Metal particles

Abstract

A method and system for detecting mercury in a hydrocarbon-containing fluid stores a sample of the hydrocarbon-containing fluid in a first reservoir. A liquid phase reagent solution is stored in a second reservoir. The liquid phase reagent solution includes nanoparticles with an affinity to mercury, wherein the nanoparticles are suspended as a colloid in the liquid phase reagent solution. The sample of the hydrocarbon-containing fluid is delivered from the first reservoir into a first port of a fluidic device while the liquid phase reagent solution is delivered from the second reservoir into a second port of the fluidic device such that the fluidic device produces slug flow. The slug flow is subject to optical analysis that determines concentration of mercury in the sample of the hydrocarbon-containing fluid.

Claims

1. A system for detecting mercury in hydrocarbon-containing fluid, comprising:

a first reservoir storing a sample of said hydrocarbon-containing fluid;

a second reservoir storing a liquid phase reagent solution comprising nanoparticles having an affinity to mercury suspended as a colloid in the liquid phase reagent solution;

a fluidic device having a first input port, a second input port, and a flow channel that includes a mixer section upstream from a reactor section, wherein the first input port is fluidly coupled to the first reservoir and receives a flow of the sample of the hydrocarbon-containing fluid delivered from the first reservoir, wherein the second input port is fluidly coupled to the second reservoir and receives a flow of the liquid phase reagent solution delivered from the second reservoir, wherein the mixer section is configured to produce slug flow from the hydrocarbon-containing fluid sample and the liquid phase reagent solution introduced into the first and second input ports, and wherein the reactor section is configured to extract mercury of the hydrocarbon-containing fluid sample where it adsorbs on the nanoparticles of the liquid phase reagent solution to form amalgam particles contained in slug flow that is produced by the fluidic device; and

an optical analyzer that analyzes the slug flow produced by the fluidic device and determines concentration of mercury in the sample of the hydrocarbon-containing fluid.

2. A system according to claim 1, further comprising:

a first pump configured to pump the sample hydrocarbon-containing fluid pumped from the first reservoir to the first input port of the fluidic device; and

a second pump configured to pump the liquid phase reagent solution from the second reservoir to the second input port of the fluidic device.

3. A system according to claim 1, wherein:

the liquid phase reagent solution includes water and water-soluble polymer that stabilizes the suspension of the nanoparticles in the liquid phase reagent solution at high temperature conditions.

4. A system according to claim 3, wherein:

the water-soluble polymer comprises at least one of poly(acrylic acid), poly(acrylamide-co-acrylic acid), poly(vinyl pyridine), poly(ethylene oxide), poly(vinyl alcohol), poly(4-styrene sulfonic acid), a poly (methacrylic acid), and poly (vinyl pyrrolidone).

5. A system according to claim 1, wherein:

the nanoparticles are formed from a noble metal, a silica core coated with a noble metal shell, a noble metal coated with a silica shell, or recursive layers of silica and a noble metal.

6. A system according to claim 1, wherein:

the nanoparticles have a concentration of up to 1×

10¹⁵ nanoparticles/cm³ in the liquid phase reagent solution.

7. A system according to claim 1, wherein:

the amalgam particles are suspended as a colloid in a liquid phase of the slug flow produced by the fluidic device.

8. A system according to claim 1, wherein:

the slug flow produced by the fluidic device is controlled by the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution supplied to the fluidic device.

9. A system according to claim 8, wherein:

the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution supplied to the fluidic device are controlled according to fluid analysis that determines the appropriate class of fluid sample type and pump control settings that dictate the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution for producing the desired slug flow.

10. A system according to claim 1, wherein:

the fluidic device further includes a third input port configured to receive a flow of a diluent and a diluter section upstream of the mixer section that dilutes the liquid phase reagent solution with the diluent introduced into the third input port; and

the mixer section is configured to produce slug flow from the hydrocarbon-containing fluid sample introduced into the first input port and the diluted liquid phase reagent solution produced by the diluter section.

11. A system according to claim 1, wherein:

the optical analyzer includes a flow-thru optical cell, a light source, a detector, and a data processing system, wherein the light source and detector perform absorption spectroscopy that measures the transmission spectrum of light for the slug flow passing through the flow-thru optical cell, and wherein the data processing system processes the transmission spectrum to determine a shift in surface plasmon resonance (SPR) peak wavelength and uses the shift in SPR peak wavelength to determine mercury concentration in the hydrocarbon-containing fluid sample.

12. A system according to claim 1, wherein:

the hydrocarbon-containing fluid sample is selected from;

a gas phase fluid sample that includes gaseous hydrocarbons, a liquid phase fluid sample that includes oil, and a gas and liquid phase fluid sample including a mixture of gaseous hydrocarbons and oil.

13. A system according to claim 1, wherein the system is part of a downhole tool configured to determine mercury concentration in a sample of formation fluid collected by the downhole tool.

14. A system according to claim 1, wherein the system is part of a surface-located facility to determine mercury concentration in fluids produced from a production well.

15. A downhole tool comprising:

a probe and flowline, wherein the probe is configured to collect formation fluid that flows into the flowline; and

the system of claim 1, fluidly coupled to the flowline, wherein the system is configured to determine mercury concentration in a sample of the formation fluid that flows into the flowline.

16. A method for detecting mercury in hydrocarbon-containing fluid, comprising:

storing a sample of the hydrocarbon-containing fluid in a first reservoir;

storing a liquid phase reagent solution in a second reservoir, wherein the liquid phase reagent solution includes nanoparticles with an affinity to mercury that are suspended as a colloid in the liquid phase reagent solution;

providing a fluidic device having a first input port, a second input port, and a flow channel that includes a mixer section upstream from a reactor section, wherein the first input port is fluidly coupled to the first reservoir, and wherein the second input port is fluidly coupled to the second reservoir;

delivering the sample of the hydrocarbon-containing fluid from the first reservoir into the first port of the fluidic device while delivering the liquid phase reagent solution from the second reservoir into the second port of the fluidic device such that the mixer section of the fluidic device produces slug flow from the hydrocarbon-containing fluid sample and the liquid phase reagent solution introduced into the first and second input ports and the reactor section of the fluidic device extracts mercury of the hydrocarbon-containing fluid sample where it adsorbs on the nanoparticles of the liquid phase reagent solution to form amalgam particles contained in slug flow that is produced by the fluidic device; and

optically analyzing the slug flow produced by the fluidic device to determine concentration of mercury in the sample of the hydrocarbon-containing fluid.

17. A method according to claim 16, wherein:

the liquid phase reagent solution includes water and water-soluble polymer that stabilizes the suspension of the nanoparticles in the liquid phase reagent solution at high temperature conditions.

18. A method according to claim 17, wherein:

the water-soluble polymer comprises at least one of poly(acrylic acid), poly(acrylamide-co-acrylic acid), poly(vinyl pyridine), poly(ethylene oxide), poly(vinyl alcohol), poly(4-styrene sulfonic acid), a poly (methacrylic acid), and poly (vinyl pyrrolidone).

19. A method according to claim 16, wherein:

the nanoparticles are formed from a noble metal, a silica core coated with a noble metal shell, a noble metal coated with a silica shell, or recursive layers of silica and a noble metal.

20. A method according to claim 16, wherein:

the nanoparticles have a concentration of up to 1×

10¹⁵ nanoparticles/cm³ in the liquid phase reagent solution.

21. A method according to claim 16, wherein:

the amalgam particles are suspended as a colloid in a liquid phase of the slug flow produced by the fluidic device.

22. A method according to claim 21, further comprising:

controlling the slug flow produced by the fluidic device by control of the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution supplied to the fluidic device.

23. A method according to claim 22, further comprising:

controlling the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution supplied to the fluidic device based on fluid analysis that determines the appropriate class of fluid sample type and pump control settings that dictate the flow rate of the hydrocarbon-containing fluid sample and the flow rate of the liquid phase reagent solution for producing the desired slug flow.

24. A method according to claim 16, further comprising:

delivering a diluent into a third port of the fluidic device for dilution of the liquid phase reagent solution such that the fluidic device produces slug flow from the hydrocarbon-containing fluid sample and the diluted liquid phase reagent solution.

25. A method according to claim 16, wherein:

the optical analyzing involves a flow-thru optical cell, a light source, a detector and a data processing system, wherein the light source and the detector perform absorption spectroscopy that measures the transmission spectrum of light for the slug flow passing through the flow-thru optical cell, and wherein the data processing system processes the transmission spectrum to determine a shift in surface plasmon resonance (SPR) peak wavelength and uses the shift in SPR peak wavelength to determine mercury concentration in the hydrocarbon-containing fluid sample.

26. A method according to claim 16, wherein:

the hydrocarbon-containing fluid sample is selected from;

a gas phase fluid sample that includes gaseous hydrocarbons, a liquid phase fluid sample that includes oil, and a gas and liquid phase fluid sample including a mixture of gaseous hydrocarbons and oil.

27. A method according to claim 16, wherein the method is carried out by a downhole tool to determine mercury concentration in a sample of formation fluid collected by the downhole tool.

28. A method according to claim 16, wherein the method is carried out by a surface-located facility to determine mercury concentration in fluids produced from a production well.

29. A system for detecting mercury in hydrocarbon-containing fluid, comprising:

a first reservoir storing a sample of said hydrocarbon-containing fluid;

a second reservoir storing a liquid phase reagent solution comprising nanoparticles having an affinity to mercury suspended as a colloid in the liquid phase reagent solution;

a fluidic device having a first input port, a second input port, a flow channel that includes a mixer means upstream from a reactor means, the first input port being fluidly coupled to the first reservoir and receiving a flow of the sample of the hydrocarbon-containing fluid delivered from the first reservoir, the second input port being fluidly coupled to the second reservoir and receiving a flow of the liquid phase reagent solution delivered from the second reservoir, the mixer means for producing slug flow from the hydrocarbon-containing fluid sample and the liquid phase reagent solution introduced into the first and second input ports, and the reactor means for extracting mercury of the hydrocarbon-containing fluid sample where it adsorbs on the nanoparticles of the liquid phase reagent solution to form amalgam particles contained in slug flow that is produced by the fluidic device; and

an optical analyzer that analyzes the slug flow produced by the fluidic device and determines concentration of mercury in the sample of the hydrocarbon-containing fluid.

30. A system according to claim 29, wherein the mixing means comprising a junction with a plurality of inlet flow paths and an outlet flow path leading to the reactor means, wherein the plurality of inlet flow paths includes a first flow path that carries the flow of the sample of the hydrocarbon-containing fluid and a second flow path that carries the flow of the liquid phase reagent solution.

31. A system according to claim 29, wherein the reactor means comprises a flow path with a non-linear path.

32. A system according to claim 29, wherein:

the optical analyzer includes a flow-thru optical cell, a light source, a detector, and a data processing system, wherein the light source and detector perform absorption spectroscopy that measures the transmission spectrum of light for the slug flow passing through the flow-thru optical cell, and wherein the data processing system processes the transmission spectrum to determine a shift in surface plasmon resonance (SPR) peak wavelength and uses the shift in SPR peak wavelength to determine mercury concentration in the hydrocarbon-containing fluid sample.