Methods for estimating properties of hydrocarbons comprising asphaltenes based on their solubility
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
G01N-033/24
C10G-007/12
G01N-030/02
출원번호
US-0152661
(2014-01-10)
등록번호
US-9458389
(2016-10-04)
발명자
/ 주소
Schabron, John F.
Rovani, Jr., Joseph F.
출원인 / 주소
The University of Wyoming Research Corporation
대리인 / 주소
Santangelo Law Offices, P.C.
인용정보
피인용 횟수 :
3인용 특허 :
18
초록▼
Disclosed herein is a method of estimating a property of a hydrocarbon comprising the steps of: preparing a liquid sample of a hydrocarbon, the hydrocarbon having asphaltene fractions therein; precipitating at least some of the asphaltenes of a hydrocarbon from the liquid sample with one or more pre
Disclosed herein is a method of estimating a property of a hydrocarbon comprising the steps of: preparing a liquid sample of a hydrocarbon, the hydrocarbon having asphaltene fractions therein; precipitating at least some of the asphaltenes of a hydrocarbon from the liquid sample with one or more precipitants in a chromatographic column; dissolving at least two of the different asphaltene fractions from the precipitated asphaltenes during a successive dissolution protocol; eluting the at least two different dissolved asphaltene fractions from the chromatographic column; monitoring the amount of the fractions eluted from the chromatographic column; using detected signals to calculate a percentage of a peak area for a first of the asphaltene fractions and a peak area for a second of the asphaltene fractions relative to the total peak areas, to determine a parameter that relates to the property of the hydrocarbon; and estimating the property of the hydrocarbon.
대표청구항▼
1. A method of estimating a property of a hydrocarbon comprising the steps of: (a) preparing a liquid sample of said hydrocarbon, said hydrocarbon having asphaltenes that include different asphaltene fractions of different polarity, and selected from the group consisting of oil and asphalt;(b) inten
1. A method of estimating a property of a hydrocarbon comprising the steps of: (a) preparing a liquid sample of said hydrocarbon, said hydrocarbon having asphaltenes that include different asphaltene fractions of different polarity, and selected from the group consisting of oil and asphalt;(b) intentionally precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants, within a substantially chemically inert stationary phase in a chromatographic column;(c) dissolving at least two of said different asphaltene fractions from said precipitated asphaltenes during a successive dissolution protocol that uses dissolving solvents of increasing strength;(d) eluting said at least two different dissolved asphaltene fractions from said chromatographic column;(e) monitoring the amount of said fractions eluted from said chromatographic column with a liquid chromatography detector that generates a detector signal for each said eluted fraction, wherein each of said signals is related to the amount of a respective one of said eluted fractions;(f) using said signals to calculate at least one separation profile peak value for a first of said asphaltene fractions wherein said at least one separation profile peak value is derived from at least one of said signals, to determine a solubility-related parameter; and(g) estimating said property of said hydrocarbon based on said solubility-related parameter,wherein said property of said hydrocarbon is selected from the group consisting of sediment content, oil processability, asphaltene content, polarity based makeup, proximity to coke formation, oil stability, reserve pyrolysis capacity, severity of pyrolysis, degree of thermal treatment, residue amount, asphaltene amount, asphaltene fraction amount, coke amount, pre-coke amount, insoluble material amount, and soluble material amount. 2. The method as described in claim 1 wherein said sediment content is selected from the group consisting of: residue material, asphaltene material, pre-coke material, coke material, and insoluble material. 3. The method as described in claim 1 wherein said step of estimating said property comprises the step of estimating processability. 4. The method as described in claim 3 wherein said step of estimating processability comprises the step of estimating catalyst activity performance. 5. The method as described in claim 1 further comprising the step of (h) repeating said steps (a)-(g) for at least one additional hydrocarbon. 6. The method as described in claim 1 wherein said step of preparing a liquid sample comprises the step of adding a solvent to said hydrocarbon. 7. The method as described in claim 1 wherein said oil is selected from the group consisting of: product oil, processed oil, pipeline oil, recovered oil, produced oil, crude oil, hydroprocessed oil, hydrocracked oil, distilled oil, heated oil, pyrolyzed oil, visbroken oil, analyzed feed oil, residua oil and catalysis processed oil. 8. The method as described in claim 1 wherein performance of said step of estimating said property generates an estimated property, and wherein said estimated property is useful in controlling a process selected from the group consisting of oil processing, oil fractionating, oil production processes, oil viscosity reduction, pipeline fouling, hydrotreating, distillation, vacuum distillation, atmospheric distillation, visbreaking, blending, asphalt formation, extraction, coking onset estimation and fouling. 9. The method as described in claim 1 wherein said solubility-related parameter comprises a parameter selected from the group consisting of conventional solubility parameter, a Hansen solubility parameter, a relative asphaltene peak area ratio, a coking index, stability gage, a weight percentage of said at least one separation profile peak, Ks coking index, a ratio of peak areas, a ratio of peak heights, a ratio of a peak area to a total peak area, a ratio of sum of peak areas to a total peak area, a ratio of weight of asphaltenes, a ratio of weight of an asphaltene fraction to total asphaltene weight; a ratio of sum of weight of asphaltene fractions to total asphaltene weight; a ratio approximately related to the ratio of density of polar asphaltenes to density of maltenes; and a ratio of durations of fraction elutions. 10. The method as described in claim 1 wherein said at least one separation profile peak value comprises a value selected from the group consisting of at least one individual peak area, a total area of peaks, a time until elution, a time during elution, a time between elution, a peak height, a peak sharpness, and a peak-related ratio. 11. The method as described in claim 1 wherein said at least one separation profile peak value comprises at least two separation profile peak values. 12. The method as described in claim 11 wherein said at least two separation profile peak values comprises a first peak area value for said first of said asphaltene fractions and a second peak area for a different one said asphaltene fractions. 13. The method as described in claim 11 wherein said at least two separation profile peak values comprises a first peak area value for said first of said asphaltene fractions and a total peak area for all eluted asphaltene fractions. 14. A method of estimating the effective particle volume fraction of a hydrocarbon comprising the steps of: (a) preparing a liquid sample of said hydrocarbon, said hydrocarbon having asphaltenes that include different asphaltene fractions of different polarity, and said hydrocarbon selected from the group consisting of oil and asphalt;(b) intentionally precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column;(c) dissolving at least two of said different asphaltene fractions from said precipitated asphaltenes during a successive dissolution protocol that uses dissolving solvents of increasing strength;(d) eluting said at least two different dissolved asphaltene fractions from said chromatographic column;(e) monitoring the amount of said fractions eluted from said chromatographic column with a liquid chromatography detector that generates a detector signal for each said eluted fraction, wherein each of said signals is related to the amount of a respective one of said eluted fractions;(f) using said signals to calculate at least one separation profile peak value for a first of said asphaltene fractions, wherein said at least one separation profile peak value is derived from at least one of said signals, to determine a solubility-related parameter; and(g) estimating said effective particle volume fraction of said hydrocarbon from said solubility related parameter. 15. The method as described in claim 14 further comprising the step of using said estimated effective particle volume fraction to control or monitor a phenomenon selected from the group consisting of: viscosity, non-pyrrolitic heat induced fouling deposition, pyrolysis coke formation induction period, oil processing, oil fractionating, oil production processes, pipeline fouling, hydrotreating, distillation, vacuum distillation, atmospheric distillation, visbreaking, blending, asphalt formation, extraction, coking onset estimation and fouling. 16. The method as described in claim 14 further comprising the step of using said estimated effective particle volume fraction to estimate the viscosity of an asphalt. 17. The method as described in claim 14 further comprising the step of estimating a propensity of said hydrocarbon for non-pyrrolitic heat induced deposition from said estimated effective particle volume fraction. 18. The method as described in claim 14 further comprising the step of estimating a pyrolysis coke formation induction period for said hydrocarbon from said estimated effective particle volume fraction. 19. The method as described in claim 14 further comprising the step of predicting the propensity of said hydrocarbon for non-pyrrolitic heat induced deposition from said estimated effective particle volume fraction. 20. The method as described in claim 14 further comprising the step of predicting a pyrolysis coke formation induction period for said hydrocarbon from said estimated effective particle volume fraction. 21. The method as described in claim 14 wherein said step of preparing a liquid sample comprises the step of adding a solvent to said hydrocarbon. 22. The method as described in claim 14 wherein said oil is selected from the group consisting of: product oil, processed oil, pipeline oil, recovered oil, produced oil, crude oil, hydroprocessed oil, hydrocracked oil, distilled oil, heated oil, pyrolyzed oil, visbroken oil, analyzed feed oil, residua oil, and catalysis processed oil. 23. The method as described in claim 14 further comprising the step of (h) repeating said steps (a)-(g) for at least one additional hydrocarbon. 24. The method as described in claim 23 further comprising the step of ranking at least two hydrocarbon materials for tendency for non-pyrrolitic heat induced fouling deposition. 25. The method as described in claim 23 further comprising the step of ranking at least two hydrocarbon materials for relative pyrolysis coke formation induction period. 26. The method as described in claim 14 further comprising the step of determining total amount of said hydrocarbon that is insoluble in low polarity solvent from said peak areas. 27. The method as described in claim 26 further comprising the step of determining effective particle volume fraction of said total amount of said hydrocarbon that is insoluble in low polarity solvent. 28. The method as described in claim 27 further comprising the step of estimating speed of coke formation from said total amount of said hydrocarbon that is insoluble in low polarity solvent. 29. The method as described in claim 26 whereis said low polarity solvent is a solvent selected from the group consisting of: heptane, hexane, pentane and iso-octane. 30. The method as described in claim 14 wherein said solubility-related parameter comprises a parameter selected from the group consisting of conventional solubility parameter, a Hansen solubility parameter, a relative asphaltene peak area ratio, a coking index, stability gage, a weight percentage of said at least one separation profile peak, Ks coking index, a ratio of peak areas, a ratio of peak heights, a ratio of a peak area to a total peak area, a ratio of sum of peak areas to a total peak area, a ratio of weight of asphaltenes, a ratio of weight of an asphaltene fraction to total asphaltene weight; a ratio of sum of weight of asphaltene fractions to total asphaltene weight; a ratio approximately related to the ratio of density of polar asphaltenes to density of maltenes; and a ratio of durations of fraction elutions. 31. The method as described in claim 14 wherein said step of intentionally precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column comprises the step of intentionally precipitating at least some of said asphaltenes within a substantially chemically inert stationary phase. 32. A method of blending at least two hydrocarbons comprising the steps of: (a) preparing a liquid sample of a hydrocarbon, said hydrocarbon having asphaltenes that include different asphaltene fractions of different polarity, and said hydrocarbon selected from the group consisting of oil and asphalt;(b) intentionally precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants within a substantially chemically inert stationary phase in a chromatographic column;(c) dissolving at least two of said different asphaltene fractions from said precipitated asphaltenes during a successive dissolution protocol that uses dissolving solvents of increasing strength;(d) eluting said at least two different dissolved asphaltene fractions from said chromatographic column;(e) monitoring the amount of said fractions eluted from said chromatographic column with a liquid chromatography detector that generates a detector signal for each said eluted fraction, wherein each of said signals is related to the amount of a respective one of said eluted fractions;(f) using said signals to calculate at least one separation profile peak value for a first of said asphaltene fractions, wherein said at least one separation profile peak value is derived from at least one of said signals, to determine a solubility-related parameter;(g) estimating a property of said hydrocarbon from said solubility-related parameter;(h) repeating steps (a)-(g) for at least one other hydrocarbon; and(g) blending said hydrocarbons based on said estimated properties of said hydrocarbons to generate a hydrocarbon blend. 33. The method as described in claim 32 further comprising the step of estimating said property of said hydrocarbon blend. 34. The method as described in claim 33 wherein said step of estimating a property of said hydrocarbon blend comprises the step of estimating a property selected from the group consisting of: effective particle volume fraction, viscosity, sediment formation, and sediment content of a product oil processed from a feed oil. 35. The method as described in claim 34 wherein said sediment content is selected from the group consisting of: residue material, asphaltene material, pre-coke material, coke material, and insoluble material. 36. The method as described in claim 33 wherein said step of estimating said property of said hydrocarbon blend comprises the step of predicting processability of said hydrocarbon blend. 37. The method as described in claim 36 wherein said step of predicting processability comprises the step of predicting catalyst activity performance. 38. The method as described in claim 33 wherein said step of estimating a property of said blend comprises the step of estimating a property selected from the group consisting of viscosity of an asphalt blend, sediment formation of said blend, and sediment content of a product oil processed from a feed oil. 39. The method as described in claim 33 wherein said property of said hydrocarbon blend reflects said properties of said hydrocarbons that make up said blend. 40. The method as described in claim 32 wherein said hydrocarbon blend is selected from the group consisting of: product oil, processed oil, pipeline oil, recovered oil, produced oil, crude oil, hydroprocessed oil, hydrocracked oil, feed oil, distilled oil, heated oil, pyrolyzed oil, visbroken oil, analyzed feed oil, residua oil, catalysis processed oil, and asphalt blend. 41. The method as described in claim 32 wherein said step of estimating comprises the step of predicting sediment content of said blend, wherein said predicted sediment content is predicted from the estimated properties of the individual hydrocarbons that make up the blend. 42. The method as described in claim 41 wherein said sediment content is selected from the group consisting of: residue material, asphaltene material, pre-coke material, coke material, and insoluble material. 43. The method as described in claim 32 wherein said step of estimating said property comprises the step of estimating a property selected from the group consisting of: sediment content, residue amount, asphaltene amount, asphaltene fraction amount, coke amount, pre-coke amount, insoluble material amount, and soluble material amount, sediment content, oil processability, asphaltene content, polarity based makeup, proximity to coke formation, oil stability, reserve pyrolysis capacity, severity of pyrolysis, and degree of thermal treatment. 44. The method as described in claim 32 wherein said step of preparing a liquid sample comprises the step of adding a solvent to said hydrocarbon. 45. The method as described in claim 32 further comprising the step of determining coking index from peak areas. 46. The method as described in claim 32 wherein said step of estimating comprises the step of predicting the propensity for non-pyrrolitic heat induced deposition. 47. The method as described in claim 32 wherein said step of estimating comprises the step of predicting pyrolysis coke formation induction period. 48. The method as described in claim 32 wherein said oil is selected from the group consisting of: product oil, processed oil, pipeline oil, recovered oil, produced, crude oil, hydroprocessed oil, hydrocracked oil, distilled oil, heated oil, pyrolyzed oil, visbroken oil, analyzed feed oil, residua oil, and catalysis processed oil. 49. The method as described in claim 32 further comprising the step of ranking at least two hydrocarbon materials for tendency for non-pyrrolitic heat induced fouling deposition. 50. The method as described in claim 32 further comprising the step of ranking at least two hydrocarbons for relative pyrolysis coke formation induction period. 51. The method as described in claim 32 wherein said solubility-related parameter comprises a parameter selected from the group consisting of conventional solubility parameter, a Hansen solubility parameter, a relative asphaltene peak area ratio, a coking index, stability gage, a weight percentage of said at least one separation profile peak, Ks coking index, a ratio of peak areas, a ratio of peak heights, a ratio of a peak area to a total peak area, a ratio of sum of peak areas to a total peak area, a ratio of weight of asphaltenes, a ratio of weight of an asphaltene fraction to total asphaltene weight; a ratio of sum of weight of asphaltene fractions to total asphaltene weight; a ratio approximately related to the ratio of density of polar asphaltenes to density of maltenes; and a ratio of durations of fraction elutions. 52. The method as described in claim 32 wherein said property of said hydrocarbon is selected from the group consisting of sediment content, oil processability, asphaltene content, pyrolysis coke formation induction period, polarity based makeup, proximity to coke formation, oil stability, reserve pyrolysis capacity, propensity for non-pyrrolitic heat induced deposition severity of pyrolysis, degree of thermal treatment, residue amount, asphaltene amount, asphaltene fraction amount, coke amount, pre-coke amount, insoluble material amount, soluble material amount.
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