Hydrocarbon Analysis Methods

Abstract

A method for determining asphaltene stability in a hydrocarbon-containing material having solvated asphaltenes therein is disclosed. In at least one embodiment, it involves the steps of: (a) precipitating an amount of the asphaltenes from a liquid sample of the hydrocarbon-containing material with an alkane mobile phase solvent in a column; (b) dissolving a first amount and a second amount of the precipitated asphaltenes by changing the alkane mobile phase solvent to a final mobile phase solvent having a solubility parameter that is higher than the alkane mobile phase solvent; (c) monitoring the concentration of eluted fractions from the column; (d) creating a solubility profile of the dissolved asphaltenes in the hydrocarbon-containing material; and (e) determining one or more asphaltene stability parameters of the hydrocarbon-containing material.

What is claimed is: 
     
         1 . A method for determining an effectiveness of one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing material subjected to an elevated temperature and pressure conditions, the method comprising the steps of:
 (a) subjecting a first column having an inert packing material therein to a first set of the elevated temperature and pressure conditions comprising a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 standard atmosphere (atm);   (b) precipitating an amount of asphaltenes from a first hydrocarbon-containing material sample having solvated asphaltenes therein with one or more first asphaltene-precipitating mobile phase solvents and capturing precipitated asphaltenes in the inert packing material in the first column;   (c) dissolving an amount of the precipitated asphaltenes at a predetermined temperature with one or more first solvents having a solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa.sup.0.5 to elute a first fraction having dissolved asphaltenes therein;   (d) determining an asphaltene content of the first hydrocarbon-containing material sample by a concentration of asphaltenes in an eluted fraction from the first column;   (e) subjecting the first column or a second column having the inert packing material therein to a second set of the elevated temperature and pressure conditions, wherein the second set of the elevated temperature and pressure conditions are substantially the same conditions as the first set of the elevated temperature and pressure conditions and comprise the temperature ranging from 140 degree C. to 450 degree C. and the pressure ranging from 1 to 200 atm;   (f) precipitating an amount of asphaltenes from a second hydrocarbon-containing material sample containing one or more asphaltene dispersant additives and having solvated asphaltenes therein with one or more second asphaltene-precipitating mobile phase solvents and capturing the precipitated asphaltenes in the inert packing material in the second column;   (g) dissolving an amount of the precipitated asphaltenes at the predetermined temperature with one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a second eluted fraction having dissolved asphaltenes therein;   (h) determining the asphaltene content of the second hydrocarbon-containing material sample by the concentration of asphaltenes in the second eluted fraction from the first column or the second column; and   (i) comparing the asphaltene content of the first hydrocarbon-containing material sample with the asphaltene content of the second hydrocarbon-containing material sample to determine the effectiveness of one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in the hydrocarbon-containing material subjected to the elevated temperature and pressure conditions.   
     
     
         2 . The method of  claim 1 , wherein the first hydrocarbon-containing material sample and the second hydrocarbon-containing material sample are the same and comprise coal tars, shale oils, shale, tar sand bitumen, asphalts, light crude oil, and heavy crude oil or fractions thereof. 
     
     
         3 . The method of  claim 1 , wherein the one or more first solvents and the one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  comprise a blend containing from 0.5 wt. % to 99.5 wt. % of one or more chlorinated solvents and from 99.5 wt. % to 0.5 wt. % of one or more alcohol solvents. 
     
     
         4 . The method of  claim 1 , wherein the asphaltene content of the eluted fraction of the first hydrocarbon-containing material sample and the second hydrocarbon-containing material sample is determined by a high-performance liquid chromatograph (HPLC). 
     
     
         5 . The method of  claim 1 , wherein an amount of the one or more asphaltene dispersant additives added to the second hydrocarbon-containing material sample is from 0.1 to 50,000 mg of asphaltene dispersant additive per kilogram of the second hydrocarbon-containing material sample. 
     
     
         6 . The method of  claim 1 , further comprising a step of storing results of comparing of step (i) in a database. 
     
     
         7 . A method for reducing fouling in one or more crude hydrocarbon refinery components located within a refinery, the method comprising the steps of:
 (a) selecting one or more asphaltene dispersant additives for adding to one or more hydrocarbon-containing feedstocks to be refined, wherein a selection of the one or more asphaltene dispersant additives comprises receiving data corresponding to an effectiveness of the one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing material subjected to elevated temperature and pressure conditions; wherein the data is derived from:   (i) subjecting a first column having an inert packing material therein to a first set of the elevated temperature and pressure conditions comprising a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 atm;   (ii) precipitating an amount of asphaltenes from a first hydrocarbon-containing material sample having solvated asphaltenes therein with one or more first asphaltene-precipitating mobile phase solvents and capturing precipitated asphaltenes in the inert packing material in the first column;   (iii) dissolving an amount of the precipitated asphaltenes at a predetermined temperature with one or more first solvents having a solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a first fraction having dissolved asphaltenes therein;   (iv) determining an asphaltene content of the first hydrocarbon-containing material sample by a concentration of asphaltenes in an eluted fraction from the first column;   (v) subjecting the first column or a second column having the inert packing material therein to a second set of elevated temperature and pressure conditions, wherein the second set of the elevated temperature and pressure conditions are substantially the same conditions as first set of the elevated temperature and pressure conditions and comprise a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 atm;   (vi) precipitating an amount of asphaltenes from a second hydrocarbon-containing material sample containing the one or more asphaltene dispersant additives and having solvated asphaltenes therein with one or more second asphaltene-precipitating mobile phase solvents and capturing the precipitated asphaltenes in the inert packing material in the second column;   (vii) dissolving an amount of the precipitated asphaltenes at the predetermined temperature with one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a second eluted fraction having dissolved asphaltenes therein;   (viii) determining the asphaltene content of the second hydrocarbon-containing material sample by the concentration of asphaltenes in the second eluted fraction from the first column or the second column; and   (ix) comparing the asphaltene content of the first hydrocarbon-containing material sample with the asphaltene content of the second hydrocarbon-containing material sample;
 (b) adding one or more of selected asphaltene dispersant additives from step (a) to the one or more hydrocarbon-containing feedstocks to be refined; and 
 (c) feeding the one or more hydrocarbon-containing feedstocks to the one or more crude hydrocarbon refinery components. 
   
     
     
         8 . The method of  claim 7 , wherein an amount of the one or more asphaltene dispersant additives added to the second hydrocarbon-containing material sample is from 0.1 to 50,000 mg of asphaltene dispersant additive per kilogram of the second hydrocarbon-containing material sample. 
     
     
         9 . The method of  claim 7 , wherein the one or more crude hydrocarbon refinery components are selected from the group consisting of a heat exchanger, a furnace, a crude preheater, a coker preheater, a FCC slurry bottom, a debutanizer exchanger, a debutanizer tower, a feed/effluent exchanger, a furnace air preheater, a flare compressor component, a steam cracker, a steam reformer, a distillation column, a fractionation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker, a storage tank and a visbreaker. 
     
     
         10 . A system capable of experiencing fouling conditions associated with particulate or asphaltene fouling, the system comprising:
 (a) one or more crude hydrocarbon refinery components; and   (b) one or more hydrocarbon-containing feedstocks containing one or more asphaltene dispersant additives therein for providing a hydrocarbon-containing feedstock having a stable plurality of asphaltene components, wherein the one or more hydrocarbon-containing feedstocks are in fluid communication with the one or more crude hydrocarbon refinery components, and further wherein a selection of the one or more asphaltene dispersant additives comprises receiving data corresponding to an effectiveness of the one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing feedstock subjected to an elevated temperature and pressure conditions; wherein the data is derived from:
 (i) subjecting a first column having an inert packing material therein to a first set of the elevated temperature and pressure conditions comprising a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 atm; 
 (ii) precipitating an amount of asphaltenes from a first hydrocarbon-containing feedstock sample having solvated asphaltenes therein with one or more first asphaltene-precipitating mobile phase solvents and capturing precipitated asphaltenes in the inert packing material in the first column; 
 (iii) dissolving an amount of the precipitated asphaltenes at a predetermined temperature with one or more first solvents having a solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a first fraction having dissolved asphaltenes therein; 
 (iv) determining an asphaltene content of the first hydrocarbon-containing feedstock sample by a concentration of asphaltenes in an eluted fraction from the first column; 
 (v) subjecting the first column or a second column having the inert packing material therein to a second set of elevated temperature and pressure conditions, wherein the second set of the elevated temperature and pressure conditions are substantially the same conditions as the first set of the elevated temperature and pressure conditions and comprise the temperature ranging from 140 degree C. to 450 degree C. and the pressure ranging from 1 to 200 atm; 
 (vi) precipitating an amount of asphaltenes from a second hydrocarbon-containing feedstock sample containing the one or more asphaltene dispersant additives and having solvated asphaltenes therein with one or more second asphaltene-precipitating mobile phase solvents and capturing the precipitated asphaltenes in the inert packing material in the second column; 
 (vii) dissolving an amount of the precipitated asphaltenes at the predetermined temperature with one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a second eluted fraction having dissolved asphaltenes therein; 
 (viii) determining the asphaltene content of the second hydrocarbon-containing feedstock sample by the concentration of asphaltenes in the second eluted fraction from the first column or the second column; and 
 (ix) comparing the asphaltene content of the first hydrocarbon-containing feedstock sample with the asphaltene content of the second hydrocarbon-containing feedstock sample. 
   
     
     
         11 . The system of  claim 10 , wherein an amount of the one or more asphaltene dispersant additives added to the second hydrocarbon-containing feedstock sample is from 0.1 to 50000 mg of asphaltene dispersant additive per kilogram of the second hydrocarbon-containing feedstock sample. 
     
     
         12 . The system of  claim 10 , wherein the one or more crude hydrocarbon refinery components are selected from the group consisting of a heat exchanger, a furnace, a crude preheater, a coker preheater, a FCC slurry bottom, a debutanizer exchanger, a debutanizer tower, a feed/effluent exchanger, a furnace air preheater, a flare compressor component, a steam cracker, a steam reformer, a distillation column, a fractionation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker, a storage tank and a visbreaker. 
     
     
         13 . A method comprising the steps of:
 (a) selecting one or more asphaltene dispersant additives for adding to a hydrocarbon-containing feedstock, wherein a selection of the one or more asphaltene dispersant additives comprises receiving data corresponding to an effectiveness of the one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing feedstock subjected to an elevated temperature and pressure conditions; wherein the data is derived from:
 (i) subjecting a first column having an inert packing material therein to a first set of the elevated temperature and pressure conditions comprising a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 atm; 
 (ii) precipitating an amount of asphaltenes from a first hydrocarbon-containing feedstock sample having solvated asphaltenes therein with one or more first asphaltene-precipitating mobile phase solvents and capturing precipitated asphaltenes in the inert packing material in the first column; 
 (iii) dissolving an amount of the precipitated asphaltenes at a predetermined temperature with one or more first solvents having a solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a first fraction having dissolved asphaltenes therein; 
 (iv) determining an asphaltene content of the first hydrocarbon-containing feedstock sample by a concentration of asphaltenes in an eluted fraction from the first column; 
 (v) subjecting the first column or a second column having the inert packing material therein to a second set of elevated temperature and pressure conditions, wherein the second set of the elevated temperature and pressure conditions are substantially the same conditions as the first set of the elevated temperature and pressure conditions and comprise the temperature ranging from 140 degree C. to 450 degree C. and the pressure ranging from 1 to 200 atm; 
 (vi) precipitating an amount of asphaltenes from a second hydrocarbon-containing feedstock sample containing the one or more asphaltene dispersant additives and having solvated asphaltenes therein with one or more second asphaltene-precipitating mobile phase solvents and capturing the precipitated asphaltenes in the inert packing material in the second column; 
 (vii) dissolving an amount of the precipitated asphaltenes at the predetermined temperature with one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a second eluted fraction having dissolved asphaltenes therein; 
 (viii) determining the asphaltene content of the second hydrocarbon-containing feedstock sample by the concentration of asphaltenes in the second eluted fraction from the first column or the second column; and 
 (ix) comparing the asphaltene content of the first hydrocarbon-containing feedstock sample with the asphaltene content of the second hydrocarbon-containing feedstock sample; and 
   (b) injecting one or more selected asphaltene dispersant additives into a well, a wellhead or a production line proximate the wellhead.   
     
     
         14 . The method of  claim 13 , wherein an amount of the one or more asphaltene dispersant additives added to the second hydrocarbon-containing feedstock sample is from 0.1 to 50000 mg of asphaltene dispersant additive per kilogram of the second hydrocarbon-containing feedstock sample. 
     
     
         15 . A method comprising the steps of:
 (a) selecting a concentration of one or more asphaltene dispersant additives for adding to a hydrocarbon-containing feedstock, wherein a selection of the concentration of the one or more asphaltene dispersant additives comprises receiving data corresponding to an effectiveness of the concentration of the one or more asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing feedstock subjected to an elevated temperature and pressure conditions; wherein the data is derived from:
 (i) subjecting a first column having an inert packing material therein to a first set of the elevated temperature and pressure conditions comprising a temperature ranging from 140 degree C. to 450 degree C. and a pressure ranging from 1 to 200 atm; 
 (ii) precipitating an amount of asphaltenes from a first hydrocarbon-containing feedstock sample having solvated asphaltenes therein with one or more first asphaltene-precipitating mobile phase solvents and capturing precipitated asphaltenes in the inert packing material in the first column; 
 (iii) dissolving an amount of the precipitated asphaltenes at a predetermined temperature with one or more first solvents having a solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a first fraction having dissolved asphaltenes therein; 
 (iv) determining an asphaltene content of the first hydrocarbon-containing feedstock sample by a concentration of asphaltenes in an eluted fraction from the first column; 
 (v) subjecting the first column or a second column having the inert packing material therein to a second set of elevated temperature and pressure conditions, wherein the second set of the elevated temperature and pressure conditions are substantially the same conditions as the first set of the elevated temperature and pressure conditions and comprise the temperature ranging from 140 degree C. to 450 degree C. and the pressure ranging from 1 to 200 atm; 
 (vi) precipitating an amount of asphaltenes from a second hydrocarbon-containing feedstock sample containing one or more asphaltene dispersant additives and having solvated asphaltenes therein with one or more second asphaltene-precipitating mobile phase solvents and capturing the precipitated asphaltenes in the inert packing material in the second column; 
 (vii) dissolving an amount of the precipitated asphaltenes at the predetermined temperature with one or more second solvents having the solubility parameter of at least 21 MPa 0.5  but no greater than 30 MPa 0.5  to elute a second eluted fraction having dissolved asphaltenes therein; 
 (viii) determining the asphaltene content of the second hydrocarbon-containing feedstock sample by the concentration of asphaltenes in the second eluted fraction from the first column or the second column; and 
 (ix) comparing the asphaltene content of the first hydrocarbon-containing feedstock sample with the asphaltene content of the second hydrocarbon-containing feedstock sample; and (b) injecting the selection of the concentration of the one or more asphaltene dispersant additives into a well, a wellhead, a production line proximate the wellhead or a refinery line susceptible to fouling. 
   
     
     
         16 . An analysis method for determining asphaltene content of a sample of a hydrocarbonaceous material that comprises an additive, comprising the steps of:
 subjecting a first column having inert stationary phase therein to a set of elevated temperature and pressure conditions;   precipitating asphaltenes of said hydrocarbon sample within said first column using one or more precipitant solvents, and capturing said precipitated asphaltenes within said first column;   dissolving an amount of the precipitated asphaltenes with one or more first dissolving solvents;   eluting from said first column an eluted fraction having dissolved asphaltenes therein; and   determining an asphaltene content of said sample from the concentration of asphaltenes in said eluted fraction.   
     
     
         17 . The method of  claim 16  wherein said elevated temperature and pressure conditions comprise temperature from 140 C to 450 C and pressure from 1 to 200 atm. 
     
     
         18 . The method of  claim 16  wherein said elevated temperature and pressure conditions comprise pressure from 50 psi to 500 psi. 
     
     
         19 . The method of  claim 16  wherein said elevated temperature and pressure conditions comprise pressure from 50 psi to 12,000 psi. 
     
     
         20 . The method of  claim 16  wherein said one or more first dissolving solvents has a solubility parameter that is greater than the solubility parameter of the one or more precipitant solvents. 
     
     
         21 . The method of  claim 16  wherein said one or more first dissolving solvents has a solubility parameter of at least 21 MPa 0.5  but not greater than 30 MPa 0.5 . 
     
     
         22 . The method of  claim 16  wherein said step of determining asphaltene content is performed, at least in part, using high performance liquid chromatography equipment. 
     
     
         23 . The method of  claim 16  wherein said additive is an asphaltene dispersant additive. 
     
     
         24 . The method of  claim 23  wherein said method is a method of determining the effectiveness of said asphaltene dispersant additive. 
     
     
         25 . The method of  claim 24  wherein said method is repeated on a hydrocarbonaceous material that is without said asphaltene dispersant additive, and wherein said effectiveness of said asphaltene dispersant additive is determined by comparing asphaltene content of said hydrocarbonaceous material without said asphaltene dispersant additive with asphaltene content of said hydrocarbonaceous material that comprises said asphaltene dispersant additive. 
     
     
         26 . The method of  claim 24  wherein said method is also an asphaltene dispersant additive selection method and is repeated on at least one additional hydrocarbonaceous material having therein a different asphaltene dispersant additive, and wherein results are used to select an asphaltene dispersant additive for an application. 
     
     
         27 . The method of  claim 26  wherein said method is also a fouling reduction method and further comprises the step of using a selected asphaltene dispersant additive to reduce fouling. 
     
     
         28 . The method of  claim 27  wherein said step of using said asphaltene dispersant additive to reduce fouling comprises the step of adding it to a production line, a well, wellhead, or production line proximate the wellhead. 
     
     
         29 . The method of  claim 16  wherein said method is a method of determining the effectiveness of said additive. 
     
     
         30 . The method of  claim 29  wherein said method is repeated on a hydrocarbonaceous material that is without said additive, and wherein said effectiveness of said additive is determined by comparing asphaltene content of said hydrocarbonaceous material without said additive with asphaltene content of said hydrocarbonaceous material that comprises said additive. 
     
     
         31 . The method of  claim 29  wherein said method is also an additive selection method and is repeated on at least one additional hydrocarbonaceous material having therein a different additive, and wherein results are used to select an additive for an application.