Method and system for marking and determining the authenticity of liquid hydrocarbons

• US 20040248307A1
• Filed: 03/08/2004
• Published: 12/09/2004
• Est. Priority Date: 06/04/2001
• Status: Active Grant

• Current Assignee: Atomic Energy Commission, State Of Isreal
• Original Assignee: Atomic Energy Commission, State Of Isreal
• Inventors: Ben-itzhak, Uziel, Sosehin, Moshe, Grof, Yair
• Granted Patent: US 8,158,432 B2
• Time in Patent Office: Days
• US Class Current: 436/56
• CPC Class Codes: G01N 33/2882 Markers marking of fuels C10L1/003
• CPC Class Codes: Y10T 436/13 Tracers or tags

Abstract

System (50) for marking a fluid by a marker, the fluid flowing from a source to a destination, the system including a sensor (58) for determining a value of a fluid property and a fluid flow controller (54) for admitting a selected amount of the marker to the fluid, wherein the selected amount is determined according to the fluid value and a predetermined concentration of the marker in the fluid in the destination.

Claims

1. System for marking a a hydrocarbon fluid by at least one marker, for determining authenticity of the fluid, the fluid flowing from a source to a destination, the system comprising:

at least one sensor for determining a fluid value of at least one fluid property of said fluid; and

at least one fluid flow controller for admitting a selected amount of said at least one marker to said fluid,

wherein said selected amount is determined according to said fluid value and a predetermined concentration of said at least one marker in said fluid; and

wherein said controller admits said at least one marker to said fluid, thereby instantaneously producing marked fluid at said predetermined concentration.

2. The system according to claim 1, further comprising a processor coupled with said at least one sensor and with said at least one fluid flow controller, wherein said processor determines said selected amount according to said fluid value and said predetermined concentration, and

wherein said processor directs said at least one fluid flow controller to admit said selected amount to said fluid.

3. The system according to claim 1, further comprising at least another sensor for determining a marker value of at least one marker property of said at least one marker, wherein said selected amount is determined according to said marker value.

4. The system according to claim 3, further comprising a processor coupled with said at least one sensor, said at least another sensor and with said at least one fluid flow controller, wherein said processor determines said selected amount according to said fluid value, said marker value and said predetermined concentration, and

wherein said processor directs said at least one fluid flow controller to admit said selected amount to said fluid.

5. The system according to claim 1, wherein said at least one fluid flow controller is selected from the list consisting of:

pump; and

valve.

6. The system according to claim 5, wherein the type of said pump is selected from the list consisting of:

constant displacement; and

variable displacement.

7. The system according to claim 1, further comprising at least one diluted marker reservoir coupled with a respective one of said at least one fluid flow controller, wherein said at least one diluted marker reservoir contains said at least one marker, diluted in a diluter, and

wherein said respective at least one fluid flow controller admits a respective one of said selected amount from said at least one diluted marker reservoir to said fluid.

8. The system according to claim 7, wherein said at least one diluted marker reservoir is coupled with at least another respective one of said at least one fluid flow controller, and wherein said at least another respective fluid flow controller admits said diluter to said at least one diluted marker reservoir.

9. The system according to claim 7, wherein said diluter is said fluid.

10. The system according to claim 1, further comprising at least one marker source coupled with a respective one of said at least one fluid flow controller, said at least one marker source containing a respective one of said at least one marker.

11. The system according to claim 10, further comprising a processor coupled with said at least one sensor and with said at least one fluid flow controller,

wherein selected ones of said at least one fluid flow controller is a valve, and another one of said at least one fluid flow controller is a pump,

wherein the input of said valve is coupled with said at least one marker source,

wherein the output of said valve is coupled with said pump,

wherein said processor determines said selected amount according to said fluid value and said predetermined concentration, and

wherein said processor directs said valve and said pump to admit said selected amount to said fluid.

12. The system according to claim 10, further comprising at least one diluted marker reservoir coupled with a respective one of said at least one fluid flow controller, and with a respective one of said at least one marker source, wherein said at least one diluted marker reservoir contains said at least one marker, diluted in a diluter, and

wherein said at least one of said fluid flow controller admits a respective one of said selected amount from said at least one diluted marker reservoir to said fluid.

13. The system according to claim 12, further comprising a processor, wherein at least another one of said at least one fluid flow controller is coupled with said processor, said at least one diluted marker reservoir and with said at least one marker source,

wherein said processor directs said at least another fluid flow controller to admit said at least one marker from said at least one marker source to said at least one diluted marker reservoir.

14. The system according to claim 1, wherein said at least one marker comprises:

at least one primary marker; and

at least one secondary marker,

wherein the amount of said at least one secondary marker is substantially lower than the amount of said at least one primary marker, whereby the presence of said at least one secondary marker in said fluid, is undetectable without increasing the concentration of said at least one secondary marker in said fluid.

15. The system according to claim 14, wherein said at least one primary marker and said at least one secondary marker are different.

16. The system according to claim 14, further comprising:

at least one primary marker source containing at least one of said at least one primary marker, said at least one primary marker source being coupled with said at least one fluid flow controller; and

a secondary marker source containing at least one of said at least one secondary marker, said at least one secondary marker source being coupled with a respective one of said at least one primary marker source,

wherein said at least one secondary marker is present in said at least one primary marker source.

17. The system according to claim 16, further comprising a processor, wherein at least another one of said at least one fluid flow controller is coupled with a respective one of said at least one primary marker source, a respective one of said at least one secondary source, and with said processor, and

wherein said processor directs said at least another fluid flow controller to admit at least one of said at least one secondary marker, from said at least one secondary source to at least one of said at least one primary source.

18. The system according to claim 14, further comprising:

at least one primary marker source containing at least one of said at least one primary marker;

at least one secondary marker source containing at least one of said at least one secondary marker, said at least one secondary

marker source being coupled with a respective one of said at least one primary marker source, and

at least one diluted marker reservoir coupled with a respective one of said at least one fluid flow controller, and with said at least one primary marker source,

wherein said at least one secondary marker is present in said at least one primary marker source,

wherein said at least one diluted marker reservoir contains said at least one primary marker and said at least one secondary marker, diluted in a diluter, and

wherein said respective at least one fluid flow controller admits a respective one of said selected amount from said at least one diluted marker reservoir to said fluid.

19. The system according to claim 1, wherein said at least one sensor determines said fluid value, at a measurement point located downstream of a marker injection point, at which said at least one fluid flow controller admits said at least one marker to said fluid.

20. The system according to claim 1, wherein said at least one sensor determines said fluid value, at a measurement point located upstream of a marker injection point, at which said at least one fluid flow controller admits said at least one marker to said fluid.

21. The system according to claim 1, wherein said at least one fluid flow controller admits said selected amount, by operating for a selected period of time.

22. The system according to claim 1, wherein said at least one fluid flow controller admits said selected amount, by operating at a selected rate.

23. The system according to claim 1, wherein said predetermined concentration equals, within an acceptable range, to 3 parts per million.

24. The system according to claim 1, wherein the tolerance of said predetermined concentration approximately equals to 5% of the value of said predetermined concentration.

25. The system according to claim 1, further comprising:

a processor; and

a user interface coupled with said processor,

wherein said user interface receives a marker key from a user, and

wherein said processor determines said selected amount according to said marker key.

26. The system according to claim 25, wherein said marker key includes information selected from the list consisting of:

type of said at least one marker;

molecular structure of said at least one marker;

a combination of said at least one marker;

said predetermined concentration;

time and date of marking said fluid by said at least one marker;

geographic location of said marking; and

type and source of said fluid.

27. The system according to claim 25, wherein the type of said marker key is selected from the list consisting of:

alphanumeric code; and

bar code.

28. The system according to claim 1, further comprising:

a processor; and

a database coupled with said processor,

wherein said processor determines said selected amount, according to data included within said database.

29. The system according to claim 28, wherein said data is respective of parameters selected from the list consisting of:

operation of said at least one fluid flow controller;

type of said at least one marker;

molecular structure of said at least one marker;

said selected amount;

said predetermined concentration;

type of said at least one sensor;

a plurality of output signal values of said at least one sensor;

type of said fluid; and

marker key.

30. The system according to claim 1, further comprising

a processor;

and

a fluid type identifier coupled to said processor,

wherein said fluid type identifier determines the type of said fluid, and

wherein said processor determines said selected amount according to said type.

31. The system according to claim 30, wherein said fluid type identifier is selected from the list consisting of:

density meter; and

viscometer.

32. The system according to claim 1, wherein the type of said at least one sensor is selected from the list consisting of:

temperature sensor;

flowmeter;

viscometer;

density meter;

device for measuring dielectric constant;

spectrometer;

X-ray fluorescence analyzer;

gas chromatograph;

radiation detector;

ultrasound detector; and

a combination of the above.

33. The system according to claim 1, wherein said at least one marker is selected from the list consisting of:

a chemical compound having the general formula C_nH<sub>2n+2−

m</sub>X_m, where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C₂(H<sub>2n+1−

m</sub>C_n)₄X_m where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C<sub>n−

m</sub>H_2n+2Y_m, where n=1,2,3 . . . , m=1,2,3 . . . , m<

n; and

a chemical compound having the formula C₂(H_2n+1C<sub>n−

m</sub>)₄Y_m, where n=1,2,3 . . . , m=1,2,3 . . . ,

where “

X” and

“

Y”

designate a chemical element which can be detected by an X-ray analyzer.

34. The system according to claim 33, wherein “

X”

is a halogen selected from the list consisting of;

fluorine;

chlorine;

bromine;

iodine; and

lithium.

35. The system according to claim 33, wherein “

Y”

is selected from the list consisting of;

silicon; and

germanium.

36. The system according to claim 1, wherein the type of said at least one marker is selected from the list consisting of:

liquid;

gas;

solid body;

powder;

light emitting substance;

light absorbing substance;

radioactive;

non-radioactive; and

a combination of the above.

37. The system according to claim 1, wherein said fluid is selected from the list consisting of:

naphtha;

gasoline;

diesel fuel;

jet fuel;

kerosene;

propane;

crude oil;

lubricant;

hydraulic fluid; and

natural gas.

38. The system according to claim 1,

wherein each of said source and said destination is selected from the list consisting of:

underground oil site;

offshore oil site;

storage tank in an oil refinery;

storage tank in an electric power plant;

storage tank in an electric generator;

storage tank in a gas station;

storage tank in an oil delivery vehicle;

storage tank in a habitable facility;

storage tank in a ground motor vehicle;

storage tank in a flying vehicle; and

storage tank in a marine vehicle.

39. Method for marking a hydrocarbon fluid by a marker, for determining authenticity of the fluid, the fluid flowing from a source to a destination, the method comprising the procedures of:

measuring a property of said fluid;

determining the amount of said marker to be added to said fluid, according to said measured property and a predetermined concentration of said marker in said fluid; and

adding said determined amount to said fluid while flowing, thereby instantaneously marking said fluid at said predetermined concentration.

40. The method according to claim 39, further comprising a preliminary procedure of diluting said marker in a diluter.

41. The method according to claim 39, further comprising a preliminary procedure of preparing said marker, by adding a secondary marker to a primary marker.

42. The method according to claim 41, wherein said secondary marker is added to said primary marker, at such a low concentration, wherein the amount of said secondary marker is substantially lower than the amount of said primary marker, whereby the presence of said secondary marker in said fluid, is undetectable without increasing the concentration of said secondary marker in said fluid.

43. The method according to claim 41, further comprising a preliminary procedure of diluting said primary marker and said secondary marker in a diluter.\

44. The method according to claim 39, wherein said marker is selected from the list consisting of:

a chemical compound having the general formula C_nH<sub>2n+2−

m</sub>X_m, where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C₂(H<sub>2n+1−

m</sub>C_n)₄X_m where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C<sub>n−

m</sub>H_2n+2Y_m, where n=1,2,3 . . . , m=1,2,3 . . . , m<

n; and

a chemical compound having the formula C₂(H_2n+1C<sub>n−

m</sub>)₄Y_m, where n=1,2,3 . . . , m=1,2,3 . . . ,

where “

X” and

“

Y”

designate a chemical element which can be detected by an X-ray fluorescence analyzer.

45. The method according to claim 44, wherein said chemical element “

X”

is a halogen selected from the list consisting of;

fluorine;

chlorine;

bromine;

iodine; and

lithium.

46. The method according to claim 44, wherein said chemical element “

Y”

is a chemical element selected from the list consisting of;

silicon; and

germanium.

47. The method according to claim 41, wherein the type of each of said primary marker and said secondary marker, is selected from the list consisting of:

liquid;

gas;

solid body;

powder;

light emitting substance;

light absorbing substance;

radioactive;

non-radioactive; and

a combination of the above.

48. The method according to claim 39, wherein said determining procedure is performed according to a marker key.

49. The method according to claim 39, wherein said determining procedure includes a sub-procedure of processing said measured property, together with entries in a look-up table.

50. The method according to claim 39, wherein said determining procedure includes a sub-procedure of running an algorithm.

51. The method according to claim 39, wherein said determining procedure includes a sub-procedure of processing said measured property, according to data retrieved from a memory.

52. The method according to claim 39, wherein said adding procedure includes a sub-procedure of controlling the operation of at least one fluid flow controller.

53. The method according to claim 39, further comprising a preliminary procedure of determining the type of said fluid.

54. The method according to claim 39, further comprising a preliminary procedure of measuring said property of said marker.

55. The method according to claim 39, wherein said adding procedure is performed at a marker injection point of a conduit within which said fluid flows, and

wherein said marker injection point is located upstream of a measurement point of said conduit, at which said property is measured.

56. The method according to claim 39, wherein said adding procedure is performed at a marker injection point of a conduit within which said fluid flows, and

wherein said marker injection point is located downstream of a measurement point of said conduit, at which said property is measured.

57. The method according to claim 39, wherein said property is selected from the list consisting of:

temperature;

flow rate;

viscosity;

density; and

concentration of a substance in said fluid.

58. The method according to claim 39, wherein said fluid is selected from the list consisting of:

naphtha;

gasoline;

diesel fuel;

jet fuel;

kerosene;

propane;

crude oil;

lubricant;

hydraulic fluid; and

natural gas.

59. The method according to claim 39, wherein each of said source and said destination, is selected from the list consisting of:

underground oil site;

offshore oil site;

storage tank in an oil refinery;

storage tank in an electric power plant;

storage tank in an electric generator;

storage tank in a gas station;

storage tank in an oil delivery vehicle;

storage tank in a habitable facility;

storage tank in a ground motor vehicle;

storage tank in a flying vehicle; and

storage tank in a marine vehicle.

60. The method according to claim 39, wherein said adding procedure is performed, such that the concentration of said marker in said fluid equals, within an acceptable range, to 3 parts per million.

61. The method according to claim 60, wherein the tolerance of said concentration is approximately equal to 5% of the value of said concentration.

62. Method for determining the authenticity of a fluid, the method comprising the procedures of:

comparing the concentration of a primary marker in said fluid, with a predetermined concentration;

determining a first authenticity of said fluid, according to the outcome of said comparison;

increasing the concentration of a secondary marker in said fluid, when said first authenticity is positive;

determining the presence of said secondary marker in said fluid; and

determining a second authenticity of said fluid, according to the outcome of said procedure for determining the presence of said secondary marker.

63. The method according to claim 62, further comprising a preliminary procedure of determining said concentration.

64. The method according to claim 62, wherein said concentration is determined by a device selected from the list consisting of:

spectrometer;

X-ray fluorescence analyzer;

gas chromatograph;

radiation detector; and

ultrasound detector.

65. The method according to claim 62, wherein said first authenticity is determined to be positive, if said concentration equals, within an acceptable range, to said predetermined concentration.

66. The method according to claim 62, wherein said first authenticity is determined to be negative, if said concentration deviates from said predetermined concentration beyond an acceptable range.

67. The method according to claim 62, wherein said predetermined concentration equals, within an acceptable range, to 3 parts per million.

68. The method according to claim 62, wherein the tolerance of said predetermined concentration is approximately equal to 5% of the value of said predetermined concentration.

69. The method according to claim 62, wherein the value of said predetermined concentration is included in a marker key.

70. The method according to claim 62, wherein the value of said predetermined concentration is included in a memory.

71. The method according to claim 62, wherein said fluid is selected from the list consisting of:

naphtha;

gasoline;

diesel fuel;

jet fuel;

kerosene;

propane;

crude oil;

lubricant;

hydraulic fluid; and

natural gas.

72. The method according to claim 62, wherein the source of said fluid is selected from the list consisting of:

underground oil site;

offshore oil site;

storage tank in an oil refinery;

storage tank in an electric power plant;

storage tank in an electric generator;

storage tank in a gas station;

storage tank in an oil delivery vehicle;

storage tank in a habitable facility;

storage tank in a ground motor vehicle;

storage tank in a flying vehicle; and

storage tank in a marine vehicle.

73. The method according to claim 62, wherein at least one of said primary marker and of said secondary marker is selected from the list consisting of:

a chemical compound having the general formula C_nH<sub>2n+2−

m</sub>X_m, where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C₂(H<sub>2n+1−

m</sub>C_n)₄X_m where n=1,2,3 . . . , m=1,2,3 . . . ;

a chemical compound having the general formula C<sub>n−

m</sub>H_2n+2Y_m, where n=1,2,3 . . . , m=1,2,3 . . . , m<

n; and

a chemical compound having the formula C₂(H_2n+1C<sub>n−

m</sub>)₄Y_m, where n=1,2,3 . . . , m=1,2,3 . . . ,

where “

X” and

“

Y”

designate a chemical element which can be detected by an X-ray fluorescence analyzer.

74. The method according to claim 73, wherein said chemical element “

X”

is a halogen selected from the list consisting of;

fluorine;

chlorine;

bromine;

iodine; and

lithium.

75. The method according to claim 73, wherein said chemical element “

Y”

is a chemical element selected from the list consisting of;

silicon; and

germanium.

76. (Cancelled)

77. (Cancelled)

78. (Cancelled)