Dual x-ray fluorescence spectrometer and method for fluid analysis

• US 6,859,517 B2
• Filed: 04/22/2003
• Issued: 02/22/2005
• Est. Priority Date: 04/22/2003
• Status: Expired due to Fees

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Wilson, Bary W., Shepard, Chester L.
• Primary Examiner(s): Glick, Edward J.
• Assistant Examiner(s): SONG, HOON K
• Application Number:
  US10/420,460
• Publication Number:
  US 20040213373A1
• Time in Patent Office: 672 Days
• Field of Search: 378/42, 378 44- 50
• US Class Current: 378/47
• CPC Class Codes: G01N 2223/076 X-ray fluorescence
• CPC Class Codes: G01N 23/223 by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
• CPC Class Codes: G01N 33/2858 Metal particles

Abstract

Disclosed are an X-ray fluorescence (SRF) spectrometer and method for on-site and in-line determination of contaminant elements in lubricating oils and in fuel oils on board a marine vessel. An XRF source block 13 contains two radionuclide sources 16, 17 (e.g. Cd 109 and Fe 55), each oriented 180 degrees from the other to excite separate targets. The Cd 109 source 16 excites sample lube oil flowing through a low molecular weight sample line 18. The Fe 55 source 17 excites fuel oil manually presented to the source beam inside a low molecular weight vial 26 or other container. Two separate detectors A and B are arranged to detect the fluorescent x-rays from the targets, photons from the analyte atoms in the lube oil for example, and sulfur identifying x-rays from bunker fuel oil for example. The system allows both automated in-line and manual on-site analysis using one set of signal processing and multi-channel analyzer electronics 34, 37 as well as one computer 39 and user interface 43.

Claims

1. An x-ray fluorescence spectrometer for on-site determination of presence of some elements in flowing fluids and some elements in batch samples of fluids comprising:

a sampler body having a first passageway therein for passage of flowing fluid through the body, and

said sampler body having a receiver therein for receiving a batch sample of a fluid;

a first x-ray radiation source located in said body;

a second x-ray radiation source located in said body;

a second passageway located in said body and communicating between said first x-ray source and said first passageway;

a third passageway located in said body and communicating between said second x-ray source and said batch sample receiver;

a first radiation detector coupled to said body and having a signal output means;

a fourth passageway located in said body and communicating between said first passageway and said first radiation detector;

a second radiation detector coupled to said body and having signal output means;

a fifth radiation response passageway located in said body and communicating between said batch receiver and said second radiation detector;

a signal processor having inputs coupled to said output means and receiving signals from said detectors, and having output means;

an analyzer having an input coupled to said signal processor output means and operable to analyze signals from said processor and produce output signals representing certain chemical components of said flowing fluid and certain chemical components of said fluid batch samples; and

a computer having an input coupled to said analyzer and an output to at least one interface for using the results of analysis by said analyzer of said signals from said processor.

2. The spectrometer of claim 1 wherein:

said first and second passageways are in a portion of said body made of material forming a shield to radiation from said first x-ray source except through said second passageway to said first passageway;

said third passageway and said receiver are in a portion of said body made of material forming a shield to radiation from said second x-ray source except through said third passageway to said receiver.

3. The spectrometer of claim 2 wherein:

said second and third passageways have colinear axes;

said first source is at an end of said second passageway;

said second source is at an end of said third passageway and is proximate said first source.

4. The spectrometer of claim 3 wherein:

said fourth passageway is located in a portion of said body made of material forming a shield to radiation from fluid flowing in said first passageway and excited by radiation from said first source; and

said fifth passageway is located in a portion of said body made of material forming a shield to radiation from a sample fluid in said receiver and excited by radiation from said second source.

5. The spectrometer of claim 4 wherein:

at least a portion of said body material is selected from the group consisting of tungsten, lead, aluminum, and plastic.

6. The spectrometer of claim 4 wherein;

said first source is cadmium 109 and said second source is iron 55.

7. The spectrometer of claim 3 wherein:

the body material in which said first passageway is located is different than the body material in which said second passageway is located.

8. The spectrometer of claim 1 wherein:

said computer also has output coupled to said analyzer to control sampling and processing events for said flowing fluid and said fluid batch sample on a time sharing basis.

9. The spectrometer of claim 1 wherein:

said analyzer is a multi channel analyzer for analyzing flowing fluid excitation response to signals received from said processor and which are derived from said first detector, and separately analyzing batch sample fluid excitation response signals received from said processor and which are derived from said second detector, whereby simultaneous analysis of flowing fluid in said first passageway and of fluid in a batch sample arc enabled.

10. The spectrometer of claim 1 wherein:

the flowing fluid is a lubricating oil flowing through an operating engine; and

the batch sample fluid is fuel for said engine.

25. In a system including a flowing fluid and storage for a separate fluid, apparatus for sampling and analyzing said flowing fluid and for sampling and analyzing said separate fluid comprising:

the x-ray fluorescence spectrometer of claim 1;

a flowing fluid and a pump moving said flowing fluid through said first passageway of the sampler body;

a container storing said separate fluid; and

a batch sample of said separate fluid from said storage container and disposed in said batch sample receiver in said body.

26. The apparatus of claim 25 wherein:

said flowing fluid is engine lubricating oil; and

said separate fluid is engine fuel oil.

27. The apparatus of claim 26 wherein:

the system is a boat and further comprises;

an engine having a lubricating oil circulating system coupled to said first passageway of the sampling body and delivering said lubricating oil through said body;

a container storing said fuel and coupled to said engine to supply fuel to said engine; and

said batch sample is fuel oil taken from said container and disposed in said receiver in said body.

28. The apparatus of claim 27 further comprising:

an engine controller coupled to said computer output and responsive to signals from said computer to change engine operation.

29. The apparatus of claim 28 and further comprising:

an annunciator coupled to said computer and responsive to results of analysis by said analyzer to alert a user.

11. An x-ray fluorescence spectrometer for on-site determination of some components in a flowing fluid target and in a stationary sample target of a different fluid comprising:

an x-ray fluorescence source block having a flowing fluid target in one location and a stationary sample fluid target in another separate location,

said block containing first and second different radionuclide sources, the first source being situated in the block to direct radiation oriented in a different direction from the direction of radiation from the second source to enable the first source to excite the flowing fluid target and enable the second source to excite the stationary sample fluid target;

two separate detectors arranged to detect fluorescent x-rays from the said flowing fluid target separately from said stationary sample fluid target;

a signal processor coupled to said detectors for separate processing of signals from said detectors; and

a signal analyzer coupled to said processor for analyzing output signals from said processor to identify components in said fluids represented by the outputs from said detectors.

12. The spectrometer of claim 11 wherein:

said sources are located between said targets on a line intercepting said targets, with each source oriented to direct radiation in a direction within about 30 degrees of 180 degrees from the direction of radiation from the other source.

13. The spectrometer of claim 12 wherein:

said flowing fluid is lubricating oil and said stationary sample fluid is fuel oil;

said components to be determined are contaminants;

said spectrometer further comprising;

a passageway for said lubricating oil in said source block and exposed to said first source; and

a receiver for said stationary sample of fuel oil and exposed to said second source.

14. The spectrometer of claim 13 further comprising:

a computer coupled to said analyzer to process signals from said analyzer; and

a user interface coupled to said computer to produce human readable information derived from analysis of said oils and representing certain chemicals contained in said oils.

15. The spectrometer of claim 14 wherein:

said first source is cadmium 109 and said second source is iron 55.

16. The spectrometer of claim 14 wherein:

said computer has an input coupled to said analyzer to receive signals from said first detector and said second detector; and

said computer has an output coupled to said signal processor to schedule sampling, processing and analyzing events on a time-sharing basis for control of said analyzer to share time between analysis of signals from the processor for said first detector and analysis of signals from the processor for said second detector.

17. The spectrometer of claim 14 wherein:

said analyzer is a multi channel analyzer for simultaneous analysis of flowing oil sample and batch sample oil.

18. The spectrometer of claim 14 further comprising:

a door normally covering said receiver and inhibiting passage of radiation from said receiver outside the spectrometer, said door being manually operable to an open position; and

a sample vial of material of low molecular weight and holding a sample of a batch sample oil and enabling entry of radiation from said second source and exit of radiation from excited batch sample oil in said vial to said second detector when said door has been opened to admit said vial to said receiver and said vial is located in said receiver and exposed to radiation from said second source.

19. A method of analyzing fluids in batch samples and flowing fluids in a single instrument comprising:

providing at least two sources of X-ray radiation in a single source block;

flowing a first fluid through said source block and exposing said flowing fluid to radiation from one of said sources;

placing a sample of a second fluid in said source block and exposing said sample to radiation from said second source;

detecting radiation from flowing fluid exposed to radiation from said first source and producing an output signal representative of the radiation from said flowing fluid;

detecting radiation from the fluid sample exposed to said second source and producing an output signal representative of the radiation from said fluid sample;

coupling said signals to an analyzer; and

separately analyzing signals from said flowing fluid and signals from said fluid sample.

20. The method of claim 19 further comprising:

while analyzing signals from said flowing fluid, producing output signals representing certain chemical elements present in said flowing fluid; and

while analyzing signals from said fluid sample, producing output signals representing certain chemical elements in said fluid sample.

21. The method of claim 20 further comprising:

coupling said output signals to a machine health monitoring system.

22. The method of claim 20 further comprising:

shielding said flowing fluid from radiation from said second source; and

shielding said fluid sample from radiation from said first source.

23. The method of claim 22 further comprising:

using a second fluid of different composition from said first fluid.

24. The method of claim 23 further comprising two different isotopes for said sources.

30. A dual source x-ray fluorescence spectrometer comprising:

an x-ray fluorescence source block having first and second fluid targets in separate locations in said source block and having a plurality of passageways therein,

first and second different radionuclide sources positioned in said source block to direct radiation in different directions through the passageways in said source block wherein said first source is positioned to excite said first fluid target and said second source is positioned to excite said second fluid target;

first and second detectors arranged to detect fluorescent x-rays emitted by said first and second fluid targets respectively, wherein said detectors are positioned in said source block such that they are not in direct line of sight with said radionuclide sauces and are substantially shielded from radiation from said radionuclide sources by said source block;

a signal processor coupled to said detectors for separate processing of signals from said detectors; and

a signal analyzer coupled to said processor for analyzing output signals from said processor to identify components in said fluids represented by the outputs from said detectors.

31. The spectrometer of claim 30 and wherein:

said sources are located generally between said targets, with said first source directing radiation toward said first target in a direction between 150 and 210 degrees of the direction said second source directs radiation toward said second target.

32. The spectrometer of claim 30 and further comprising:

a computer coupled to said analyzer to process signals from said analyzer; and

a user interface coupled to said computer to produce human readable information derived from analysis of said fluid targets and representing certain chemicals contained in said fluid targets.

33. The spectrometer of claim 32 wherein:

said computer has an input coupled to said analyzer to receive signals from said first detector and said second detector; and

said computer has an output coupled to said signal processor to schedule sampling, processing and analyzing events on a time-sharing basis for control of said analyzer to share time between analysis of signals from the processor for said first detector and analysis of signals from the processor for said second detector.

34. The spectrometer of claim 33 wherein:

said analyzer is a multi channel analyzer for simultaneous analysis of flowing oil sample and batch sample oil.

35. The spectrometer of claim 33 and wherein:

at least one of said fluid targets is a flowing fluid.

36. The spectrometer of claim 33 wherein at least one of said fluid targets is a batch sample, said spectrometer further comprising a door on said housing being selectively operable to either cover or permit access to a well for receiving a batch sample vial.

37. The spectrometer of claim 30 wherein said source block defines a first noise reduction chamber positioned on a line between said first source and said first fluid target and a second noise reduction chamber positioned on a line between said second source and said second fluid target, said first and second noise reduction chambers operable to receive radiation directed from said first and second sources through the passageways and through said first and second fluid targets respectively.

38. The spectrometer of claim 37 wherein said noise reduction chambers have a size dimension relative to the line between the respective source and fluid target that is substantially greater than the size dimension of the passageway between the respective source and fluid target.

39. A dual source x-ray fluorescence spectrometer comprising:

an x-ray fluorescence source block having first and second fluid targets in separate locations in said source block and having a plurality of passageways therein,

first and second x-ray sources positioned in said source block to direct radiation in different directions through the passageways in said source block wherein said first source is operable to excite said first fluid target and said second source is operable to excite said second fluid target;

first and second detectors arranged to detect fluorescent x-rays emitted by said first and second fluid targets,

wherein said source block defines a first noise reduction chamber positioned along a first centerline of a passageway between said first fluid target and said first x-ray source with said first fluid target between said first noise reduction chamber and said first x-ray source such that x-rays from said first source that pass through said first fluid target can be received by said first noise reduction chamber,

wherein said first detector is positioned in the source block such that it does not intersect the centerline of the passageway between said first detector and said first fluid target,

a signal processor coupled to said detectors for separate processing of signals from said detectors; and

a signal analyzer coupled to said processor for analyzing output signals from said processor to identify components in said fluids represented by the outputs from said detectors.

40. The spectrometer of claim 39 wherein said source block includes first and second portions of substantially different material composition.

41. The spectrometer of claim 39 wherein said source block defines a second noise reduction chamber positioned along a second centerline of a passageway between said second fluid target and said second x-ray source with said second fluid target between said second noise reduction chamber and said second x-ray source such that x-rays from said second source that pass through said second fluid target can be received by said second noise reduction chamber.

42. The spectrometer of claim 41 wherein the first and second centerlines are substantially parallel.

43. The spectrometer of claim 39 wherein said first fluid target is contained in a flow path defined by a tube substantially transparent to x-rays from said first x-ray source.

44. The spectrometer of claim 43 wherein said second fluid target is a batch fluid sample.