Method for predicting fouling tendency of a hydrocarbon-containing feedstock
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
G01N-033/24
G01N-030/02
출원번호
US-0600039
(2012-08-30)
등록번호
US-8492154
(2013-07-23)
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 :
7인용 특허 :
15
초록▼
Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of t
Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of the precipitated asphaltenes; (c) analyzing the one or more solubility characteristics of the precipitated asphaltenes; and (d) correlating a measurement of feedstock fouling tendency for the first hydrocarbon-containing feedstock sample with a mathematical parameter derived from the results of analyzing the one or more solubility characteristics of the precipitated asphaltenes.
대표청구항▼
1. A method of determining fouling tendency of a hydrocarbon-containing feedstock comprising the steps of: (a) preparing a liquid sample of said hydrocarbon-containing feedstock, said hydrocarbon-containing feedstock having asphaltenes that include different asphaltene fractions of different polarit
1. A method of determining fouling tendency of a hydrocarbon-containing feedstock comprising the steps of: (a) preparing a liquid sample of said hydrocarbon-containing feedstock, said hydrocarbon-containing feedstock having asphaltenes that include different asphaltene fractions of different polarity;(b) 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) detecting said at least two eluted fractions with a liquid chromatography detector to generate a detector signal for each said eluted fraction; wherein said step of detecting comprises monitoring the amount of said eluted fractions from said chromatographic column with said liquid chromatography detector, and wherein said signal is proportional to the amount of each said eluted fraction,(f) using said signals to calculate a percentage of each peak area for a first amount and a second amount of dissolved asphaltenes relative to the total peak areas, wherein the peak areas are derived from the signals, to determine a parameter that relates to fouling tendency of said hydrocarbon-containing feedstock; and(g) determining said fouling tendency of said hydrocarbon-containing feedstock from said parameter. 2. The method of claim 1, wherein the hydrocarbon-containing feedstock comprises a material selected from the group consisting of oil, crude oil, asphalt, and a coal-derived product. 3. The method of claim 1, wherein said step of precipitating comprises the step of precipitating with one or more precipitants selected from the group consisting of iso-octane, pentane, heptane, hexane, and mixtures thereof. 4. The method of claim 1, wherein step (c) comprises: (i) dissolving a first amount of the precipitated asphaltenes in one or more first dissolving solvents having a solubility parameter at least 1 MPa0.5 higher than the one or more precipitants;(ii) dissolving a second amount of the precipitated asphaltenes in one or more second dissolving solvents having a solubility parameter higher than the one or more first dissolving solvents, wherein the solubility parameter of the one or more second dissolving solvents is at least about 21 MPa0.5 but no greater than about 30 MPa0.5. 5. The method of claim 4, further comprising prior to step (ii): dissolving at least part of the precipitated asphaltenes in one or more third dissolving solvents having a solubility parameter between the solubility parameter of the first dissolving solvent and the solubility parameter of the second dissolving solvent; and dissolving at least part of the precipitated asphaltenes in one or more fourth dissolving solvents having a solubility parameter between the solubility parameter of the third dissolving solvent and the solubility parameter of the second dissolving solvent. 6. The method of claim 1 wherein said step of monitoring the amount of eluted fractions from the column comprises monitoring the concentration of eluted fractions from the column with a liquid chromatography detector that generates a signal proportional to the concentration of each eluted fraction. 7. The method of claim 1, wherein step (c) comprises dissolving a first amount and a second amount of the precipitated asphaltenes by gradually and continuously changing the solvents to a final mobile phase solvent having a solubility parameter at least about 1 MPa0.5 higher than the one or more precipitants. 8. The method of claim 1, wherein step (c) comprises: (i) gradually and continuously changing the one or more precipitants to a first final mobile phase dissolving solvent having a solubility parameter at least about 1 MPa0.5 higher than the one or more precipitants to dissolve a first amount of the precipitated asphaltenes; and(ii) gradually and continuously changing the first final mobile phase dissolving solvent to a second final mobile phase dissolving solvent having a solubility parameter at least about 1 MPa0.5 higher than the first final mobile phase dissolving solvent to dissolve a second amount of the precipitated asphaltenes. 9. The method of claim 1 wherein said step of detecting said at least two eluted fractions comprises the step of detecting to generate a separation profile. 10. The method of claim 1 wherein the fouling tendency is derived from a determination of the amount of foulant deposited. 11. The method of claim 1 wherein feedstock fouling tendencies are determined thermally treating at least two feedstocks to varying degrees, then cooling said thermally treated feedstocks, and then analyzing samples of the feedstocks for high polarity asphaltene concentration to determine the effect thermally treating the feedstock has on producing high polarity asphaltenes. 12. The method of claim 1, wherein said hydrocarbon containing feedstock sample is a first hydrocarbon containing feedstock sample, and further comprising the steps of: (h) selecting one or more of the same or different hydrocarbon-containing feedstock samples; repeating steps (a)-(g); and(i) comparing the parameter of the one or more of the same or different hydrocarbon-containing feedstock samples with the parameter of the first hydrocarbon-containing feedstock sample to predict one or more leading candidate hydrocarbon-containing feedstocks relative to fouling tendency during hydroprocessing. 13. The method of claim 12 further comprising the steps of generating a cost value for the leading candidate hydrocarbon-containing feedstock samples, and comparing the cost value generated for the leading candidate hydrocarbon-containing feedstock samples with a market price of the same or different hydrocarbon containing feedstocks. 14. The method of claim 12, further comprising the step of blending the leading candidate hydrocarbon-containing feedstock with one or more different hydrocarbon-containing feedstocks. 15. The method of claim 1, wherein said hydrocarbon containing feedstock sample is a first hydrocarbon containing feedstock sample, and further comprising the step of comparing a different sample of the same first hydrocarbon-containing feedstock sample with the first hydrocarbon-containing feedstock sample for quality control of the first hydrocarbon-containing feedstock sample. 16. The method of claim 1 further comprising the steps of generating a cost value for a hydrocarbon-containing feedstock sample, and comparing said cost value generated for said hydrocarbon-containing feedstock sample with a market price of the same or different hydrocarbon-containing feedstock. 17. The method of claim 1 further comprising the step of (h) generating a price of the hydrocarbon-containing feedstock, wherein said method transforms a product development process to reduce time in bringing a product to market. 18. The method of claim 1 wherein said step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column comprises the step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column that contains a substantially inert stationary phase. 19. A method comprising the steps of: (i) selecting one or more hydrocarbon-containing feedstocks, wherein the selection of the one or more hydrocarbon-containing feedstocks comprises: (a) preparing a liquid sample of a first hydrocarbon-containing feedstock, said first hydrocarbon-containing feedstock having asphaltenes that include different asphaltene fractions of different polarity;(b) 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) detecting said at least two eluted fractions with a detector to generate detector signals;(f) using said signals to calculate a percentage of each peak area for a first amount and a second amount of dissolved asphaltenes relative to the total peak areas, wherein the peak areas are derived from the signals, to determine a parameter that relates to fouling tendency of said first hydrocarbon-containing feedstock;(g) determining said fouling tendency of said first hydrocarbon-containing feedstock from said parameter; and(ii) feeding the selected hydrocarbon-containing feedstock to one or more crude hydrocarbon refinery components. 20. The method of claim 19, further comprising (h) selecting one or more second hydrocarbon-containing feedstock samples; repeating steps (a)-(g); and comparing the parameter for the one or more second hydrocarbon-containing feedstock samples with the parameter for the first hydrocarbon-containing feedstock sample to predict one or more leading candidate hydrocarbon-containing feedstocks relative to fouling tendency during hydroprocessing. 21. The method of claim 19, wherein the one or more hydrocarbon refinery components is selected from the group consisting of a component used in oil processing, a component used in oil fractionating, a component used in oil production, a pipeline component, a hydrotreating process component, a distillation process component, a vacuum distillation process component, an atmospheric distillation process component, a visbreaking process component, a blending process component, an asphalt formation process component, an extraction component, a coking onset estimation component, a fouling component, a refinery unit, a heat exchanger, and a refinery unit other than a heat exchanger. 22. The method of claim 19 wherein said step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column comprises the step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column that contains a substantially inert stationary phase. 23. A system comprising: (i) one or more crude oil hydrocarbon refinery components; and(ii) one or more hydrocarbon-containing feedstocks in fluid communication with the one or more crude hydrocarbon refinery components, wherein the one or more hydrocarbon-containing feedstocks is selected by a process comprising the steps of: (a) preparing a liquid sample of a first hydrocarbon-containing feedstock, said first hydrocarbon-containing feedstock having asphaltenes that include different asphaltene fractions of different polarity;(b) 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) detecting said at least two eluted fractions with a detector to generate detector signals;(f) using said signals to calculate a percentage of each peak area for a first amount and a second amount of dissolved asphaltenes relative to the total peak areas, wherein the peak areas are derived from the signals, to determine a parameter that relates to fouling tendency of said hydrocarbon-containing feedstock; and(g) determining the fouling tendency of said first hydrocarbon-containing feedstock from said parameter. 24. The system of claim 23, wherein the process further comprises (h) selecting one or more second hydrocarbon-containing feedstock samples; repeating steps (a)-(g); and comparing the parameter for the one or more second hydrocarbon-containing feedstock samples with the parameter for the first hydrocarbon-containing feedstock sample to predict one or more leading candidate hydrocarbon-containing feedstocks relative to fouling tendency during hydroprocessing. 25. The system of claim 23, wherein the one or more crude hydrocarbon refinery components is selected from the group consisting of a component used in oil processing, a component used in oil fractionating, a component used in oil production, a pipeline component, a hydrotreating process component, a distillation process component, a vacuum distillation process component, an atmospheric distillation process component, a visbreaking process component, a blending process component, an asphalt formation process component, an extraction component, a coking onset estimation component, a fouling component, a refinery unit, a heat exchanger, and a refinery unit other than a heat exchanger. 26. The method of claim 24 further comprising the steps of selecting one or more second hydrocarbon-containing feedstock samples; repeating steps (i)-(vii); comparing the parameter for the one or more second hydrocarbon-containing feedstock samples with the parameter for the first hydrocarbon-containing feedstock sample to predict which of the hydrocarbon-containing feedstock samples is a leading candidate relative to fouling tendency during hydroprocessing; and selecting the leading candidate hydrocarbon containing feedstocks based on fouling tendency of the hydrocarbon containing feedstock for hydroprocessing and price. 27. The system of claim 23 wherein said step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column comprises the step of precipitating at least some of said asphaltenes from said liquid sample with one or more precipitants in a chromatographic column that contains a substantially inert stationary phase.
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