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WO2000077120A2 - Technique de prevision d'un etat proche de la cokefaction - Google Patents

Technique de prevision d'un etat proche de la cokefaction Download PDF

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Publication number
WO2000077120A2
WO2000077120A2 PCT/US2000/015950 US0015950W WO0077120A2 WO 2000077120 A2 WO2000077120 A2 WO 2000077120A2 US 0015950 W US0015950 W US 0015950W WO 0077120 A2 WO0077120 A2 WO 0077120A2
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Prior art keywords
hydrocarbon material
solvent
amount
processing
hydrocarbon
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WO2000077120A9 (fr
WO2000077120A3 (fr
Inventor
John F. Schabron
Joseph F. Rovani
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University of Wyoming Research Corp (dba Western Research Institute)
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University of Wyoming Research Corp (dba Western Research Institute)
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Priority to CA2371790A priority Critical patent/CA2371790C/fr
Priority to MXPA01012580A priority patent/MXPA01012580A/es
Priority to EP00941317A priority patent/EP1198714A4/fr
Priority to AU56036/00A priority patent/AU776038B2/en
Priority to US10/009,863 priority patent/US6773921B1/en
Publication of WO2000077120A2 publication Critical patent/WO2000077120A2/fr
Publication of WO2000077120A3 publication Critical patent/WO2000077120A3/fr
Publication of WO2000077120A9 publication Critical patent/WO2000077120A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/12—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/007—Visbreaking
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2805—Oils, i.e. hydrocarbon liquids investigating the resistance to heat or oxidation

Definitions

  • methods and apparatus for evaluating or processing hydrocarbon materials having unimodal characteristics which may acquire multimodal characteristics upon processing.
  • indica of stability for hydrocarbons having unimodal characteristics which may be used separately, or used in combination, or used in comparison to a determined threshold of instability for such unimodal characteristics, to assist in determining the proximity of hydrocarbon materials having unimodal characteristics to formation of multimodal characteristics, or to assist in pre-determining the degree of acquired multimodal characteristics in response to various processing parameters.
  • hydrocarbon materials such as heavy oils, petroleum residua, shale oils, coal tars, tar sand bitumen, asphalts, or the like
  • hydrocarbon materials such as heavy oils, petroleum residua, shale oils, coal tars, tar sand bitumen, asphalts, or the like
  • non- pyrolytic temperatures at or below 340°C or 644 °F
  • This induction period can be variable, ranging from a few seconds to hours, depending on the particular hydrocarbon material and the temperature at which it is processed.
  • refiners often process hydrocarbon materials based on arbitrary criteria. Because arbitrary criteria are used, conventional processing of hydrocarbon materials can result in product yields that may not be maximal.
  • indicia of stability with respect to the homogeneous mixture or to define thresholds of instability at which transition to the heterogenous mixture may occur.
  • Such indica of stability or thresholds of instability for hydrocarbon materials may be used, for example, to evaluate the suitability of hydrocarbon materials for particular types of processing, to predict the proximity to carbon deposition or coke formation, or for controlling hydrocarbon material processing in a manner which eliminates, minimizes, or predicts the amount of carbon deposition or coke formation.
  • a significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be the failure of conventional technology to define, provide measures for, or interpretations of, the dynamics of unimodal characteristics of intact hydrocarbon materials.
  • Unimodal characteristics define a comprehensible pattern of attributes having predictable variation to changing environmental or processing parameters. As such, unimodal characteristics make possible the development of ascertainable indicia for comparative evaluation of the functionally related components that make up a hydrocarbon material. Ascertainable indicia can make the response of hydrocarbon materials to such environmental or processing parameters predictable. Unimodal characteristics may also provide objective indica for the manufacture of hydrocarbon material products to assure that components have an anticipated degree of association. As can be understood, conventional technology has focused upon evaluation of the characteristics of separated components of hydrocarbon materials.
  • conventional technology may not provide suitable indica of stability, thresholds of instability, or the methods for comparing such indicia of stability to such thresholds of instability which are the ascertainable measures of the unimodal characteristics of intact, unseparated hydrocarbon material. Indeed, conventional technology affords few, if any, tools for diagnosing or predicting how a hydrocarbon material will behave under a specific set of circumstances.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be formation of carbon rich material during non- pyrolytic events (at or below about 340° C).
  • the deposition of carbon rich material, such as coke can result in fouling of heat exchange devices, or other refinery equipment in both upstream and downstream operations. This equipment may have to be shut down for mechanical coke removal as disclosed by Schabron, J. F. et al., Deposition From Heavy Oils, pp. viii and 2, (2000), hereby incorporated by reference.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may also be the formation of carbon rich deposits, such as coke, from pyrolytic events (at or above about 340° C). Deposition of carbon rich material, such as coke, from pyrolytic events during processing can also result in the problems described above including having to shut down processing equipment for mechanical removal of the deposited materials.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be the lack of a method or use of arbitrary criteria for predicting the proximity of a hydrocarbon material to the point of transition from a homogenous mixture of components to a heterogenous mixture of components, including the proximity to carbon deposition or coke formation.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be a low yield of liquid distillates.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be high emissions.
  • An energy savings of about 2.5-3.9 billion Btu per day, as discussed above, can result in a corresponding lowering of emissions from fuel that is not burned in processing operations.
  • residual fuel used as the heat source produces about 174 pounds of carbon dioxide per million Btu generated Department of Energy, ⁇ IT Report, pp. 27, (1998).
  • the reduction in carbon dioxide emissions for each 1 % industry-wide efficiency improvement may be about 218-679 tons per day!
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be financial losses.
  • the disruption of hydrocarbon material processing from fouling due to deposition of carbon rich material, such as coke, is pervasive throughout the industry.
  • the financial losses due to unscheduled downtime events as a result of non-pyrolytic, or of pyrolytic, deposition of carbon rich materials such as coke, may be difficult to quantify, but they are important.
  • Another significant problem with conventional technology for the evaluation and processing of hydrocarbon material may be that the liquid products of distillation may be of lower quality. Interrupting the distillation process, or proceeding with the distillation process in steps or stages, to avoid deposition of carbon rich materials or coke may allow for contamination of the liquid distillates.
  • Yet another significant problem with existing methods of processing hydrocarbon materials may be lack of a method for predicting the amount of initial deposition of carbon rich material or coke formation upon pyrolysis of a hydrocarbon material.
  • Still another significant problem with existing methods of processing of hydrocarbon materials may be the lack of apparatus or methods that are practical, convenient, or provide for real time data with respect to the stability of hydrocarbon materials.
  • Indica which define unimodal characteristics of hydrocarbon materials, or indicia which estimate the stability of such unimodal characteristics of hydrocarbon materials which may be used separately or may be used in combination, or may be used in comparison to determined threshold of instability for such unimodal characteristics, to assist in determining the proximity of such unimodal characteristics to formation of multimodal characteristics, or to assist in predicting the degree of acquired multimodal characteristics in response to various processing parameters.
  • a broad object of a particular embodiment of the invention can be to establish values for various associations between components of a hydrocarbon material which define the attributes or characteristics of a unimodal system.
  • One aspect of this object can be to provide a value for the size of a core material in comparison to the size of the core material having sufficient solvent solvation shell to maintain unimodal character (K s ).
  • a second aspect of this object can be to provide an average value for the relative size ratio of a plurality of solvated core materials to the size of the plurality of solvated core materials having sufficient associated solvent (for example trapped solvent between them) to maintain unimodal character (K F ).
  • a second broad object of a particular embodiment of the invention can be to provide indicia of stability for the above-mentioned unimodal characteristics exhibited by hydrocarbon materials.
  • Indicia of stability are values that result from measuring the degree of association between certain components in the hydrocarbon material which can allow assessment of the stability of a unimodal characteristic at a given point in time. Having objective values that reflect the instant degree of stability of the unimodal characteristics can be useful in evaluating suitability of hydrocarbon materials for various types of processing parameters, or for maintenance of unimodal characteristics during hydrocarbon processing.
  • a threshold of instability establishes a degree of association (or lack of association) between components of a hydrocarbon material at which acquisition of multimodal characteristics by the hydrocarbon material may be expected.
  • These thresholds of instability may be used in conjunction with the above- mentioned indica of stability to assess the proximity of hydrocarbon materials having unimodal characteristics to the threshold of instability or to acquisition of multimodal characteristics.
  • Another object of a particular embodiment of the invention can be to provide indicia of stability or to establish thresholds of instability based upon instrumented measurement of various size ratios which co ⁇ elate with unimodal characteristics.
  • Another object of a particular embodiment of the invention can be to provide indicia of stability related to the molecular weight of particular components in a hydrocarbon material which correlate with the stability of unimodal characteristics.
  • Another object of a particular embodiment of the invention can be to provide indicia of stability based upon the distribution of various polar components in hydrocarbon materials.
  • One aspect of this embodiment of the invention may be an indicia of stability determined as the amount of asphaltenes soluble in particular solvent having a particular polarity.
  • the amount of asphaltenes precipitated with heptane soluble in cyclohexane can be diagnostic of the stability of the unimodal character of hydrocarbon materials.
  • a second aspect of this embodiment of the invention can be an indicia of stability determined as the ratio of the weight percent of solvent soluble asphaltenes to the weight percent asphaltenes that are not solvent soluble.
  • a third aspect of this embodiment of the invention can be an indicia of stability based upon titration data. This involves the a titration of solutions of hydrocarbon material with a weak solvent to the point of asphaltene precipitation.
  • An indicia of stability can be described based on the titration data defined as p a /C m ⁇ n .
  • Another object of a particular embodiment of the invention can be to use the determined indicia of stability in comparison to the established thresholds of instability to assess the proximity of unimodal characteristics to the threshold of instability.
  • One aspect of this obj ect of the invention can be to predict the proximity of a hydrocarbon material to coke formation.
  • Another object of a particular embodiment of the invention can be to use the indicia of stability, individually or in combination to evaluate hydrocarbon materials prior to processing or during processing to model substantially continuous distillation parameters for a particular hydrocarbon material or mixture hydrocarbon materials.
  • Another object of a particular embodiment of the invention can be optimization of the yields of distillable liquids from a hydrocarbon material having unimodal characteristics. Any increase in the yield of distillable liquids from the same amount of hydrocarbon material such as heavy oil or petroleum residuum provides an immediate increase in revenue. As such, a method of optimizing yields of distillable liquids has immediate and important commercial applications.
  • Another object of a particular embodiment of the invention can be to predict the degree of multimodal characteristics that may be acquired by a particular hydrocarbon material with respect to various processing parameters.
  • One aspect of this object may be to predict the initial amount of carbon rich material, such as coke, that may be formed upon processing of a hydrocarbon material with particular processing parameters.
  • Another object of a particular embodiment of the invention can be to save energy. There may be a significant energy savings involved when a higher yield of distillates is produced from the same amount of hydrocarbon material. As described above, there may be only a minimal amount of extra heat required for a 1% improvement of distillate output at a particular temperature since the majority of the energy is used to initially heat all the hydrocarbon material for distillation. For each 1% decrease in the amount of distillate bottoms heated for a subsequent coking operation in the United States a potential savings in energy of about 2.5 billion Btu to about 3.9 billion Btu per day may be realized.
  • Another object of a particular embodiment of the invention can be to reduce emissions.
  • the above-mentioned potential savings in energy of about 2.5 billion Btu to about 3.9 billion Btu results in a corresponding reduction in emissions from fuel that is not burned in processing additional hydrocarbon material.
  • residual fuel used to as the heat source for processing produces about 174 pounds of carbon dioxide per million Btu generated.
  • the reduction in carbon dioxide emission for each 1% industry-wide efficiency improvement is about 218-679 tons.
  • Another object of a particular embodiment of the invention can be to produce higher initial quality as compared to conventional liquid distillables. Because the process of distillation may be nearly continuous, the distillates may have fewer opportunities to collect water and become otherwise contaminated. This may result in higher purity distillates and perhaps lower post distillation processing costs. As such, distillates from near continuous distillation processes made possible from the instant invention may be distinguishable from conventional distillation products.
  • Still another object of a particular embodiment of the invention can be to provide a molecular weight/polarity map system to assess the solubility of various components in a mixture of asphaltene complexes at various distillation parameters.
  • Such a map system may provide an evaluation method for diagnosing processing conditions for hydrocarbon materials having unimodal characteristics prior to or during distillation.
  • Yet another object of a particular embodiment of the invention can be to establish a sequential solvent extraction system to isolate various asphaltene complexes from hydrocarbon materials having unimodal characteristics based on molecular weight or polarity.
  • Figure 1 shows the relationship between solubility and solubility parameter difference.
  • Figure 2 shows the effects of molecular weight and solubility parameter difference on solubility.
  • Figure 3 shows a flow diagram of the hydrocarbon material solvent extraction sequence and solubility parameters of solvents.
  • Figure 4 shows a molecular weight polarity map
  • Figure 5 shows elution profiles of high performance size exclusion chromatography of various amounts of material A from fraction 4 .
  • Figure 6 shows elution profiles of high performance size exclusion chromatography of maltenes.
  • Figure 7 shows titration results for three stripper bottoms.
  • Figure 8 shows weight percent coke relative to values for the indicia of stability pa/Cm ⁇ n
  • Figure 9 shows weight percent coke relative to values for the indicia of stability /x based upon the weight percent of precipitated asphaltenes soluble in a second solvent over the weight percent of precipitated asphaltenes.
  • Figure 10 shows weight percent coke relative to values for the indicia of stability Ks .
  • Figure 11 shows weight percent coke relative to values for the indica of stability KF .
  • Figure 12 shows weight percent coke relative to values for the indica of stability ⁇ .
  • Figure 13 shows a graph of weight percent coke relative to values for the indica of stability ⁇ FS
  • Hydrocarbon materials such as heavy oils, petroleum residua, coal tars, shale oils, asphalts, or the like can comprise polar core materials, such as asphaltenes, dispersed in lower polarity solvent(s).
  • Intermediate polarity material(s) usually referred to as resin(s)
  • resin(s) can associate with the polar core materials to maintain a homogeneous mixture of the components.
  • the invention focuses on novel unimodal characteristics which are ascertainable aspects of the relationship, or degree of association, between these components that can maintain the hydrocarbon material as a homogeneous mixture.
  • the lack of, or diminishment of these ascertainable aspects of the unimodal character can be used to predict the onset or degree of acquired (and perhaps undesirable) multimodal characteristics associated with formation of the resulting heterogeneous mixture.
  • refinery processes including but not limited to, atmospheric or vacuum distillation, visbreaking, hydrocracking, delayed coking, Fluid Coking, FLEXICOKJNG, or Eureka that convert hydrocarbon materials to lighter distillate fuels require heating for distillation, hydrogen addition, or carbon rejection (coking).
  • the efficiency of converting such hydrocarbon material may be limited by transition of the hydrocarbon material of homogeneous mixture to a hydrocarbon material of heterogenous mixture.
  • the transition to the heterogenous mixture may include the formation of insoluble carbon-rich coke deposits, including the formation of coke.
  • any reduction in carbon deposition, or increase in the distillation yield during the thermal processing of hydrocarbon material can have a significant impact on the manner or economics of hydrocarbon processing.
  • the invention in contrast to conventional processing technology, provides ascertainable unimodal characteristics as the basis for measures of stability with respect to hydrocarbon materials that transit between homogenous mixtures and heterogenous mixtures of components, methods for assessing the degree of the such unimodal characteristics, methods for predicting the proximity of hydrocarbon materials having unimodal characteristics from the threshold of acquiring multimodal characteristics, or methods for predicting the degree of multimodal characteristics acquired due to various processing parameters.
  • the invention provides indicia of stability, thresholds of instability, methods for comparing such indicia of stability with such thresholds of instability so that hydrocarbon materials can be evaluated for processing, for selecting processing parameters to avoid carbon deposition, or for reaching predetermined levels of carbon deposition, for increasing the yield of liquid distillates, for decreasing emissions from processing, or for reducing the consumption of energy.
  • each are disclosed as part of the results shown to be achieved by the various methods and devices described and as steps which are inherent to utilization.
  • steps which are inherent to utilization are inherent to utilization.
  • steps which are inherent to utilization are inherent to utilization.
  • a variety of methods are disclosed, it should be understood that these are accomplished using certain devices but also that the methods and devices can varied in a number of ways. Importantly, as to all of the foregoing, all of these facets should be understood to be encompassed by this disclosure.
  • ⁇ G is the free energy
  • ⁇ H is the heat of mixing
  • T is the temperature
  • ⁇ S is the change in entropy.
  • the entropy term is relatively large, and the heat of mixing determines if the mixing will occur.
  • the heat of mixing may be described as:
  • ⁇ H V (( ⁇ EJV/ 2 - ( ⁇ E 2 /V 2 ) ' ⁇ ) 2 ⁇ , ⁇
  • ⁇ H is the heat of mixing
  • N is total volume
  • ⁇ E X is the molar energy of vaporization of component x
  • V x is the molar volume of component x
  • ⁇ x is the volume fraction of component x in the solution.
  • group contributions can be used to calculate if the density of the material is known or can be estimated.
  • the heat of mixing two materials is dependent on the difference between their solubility parameters squared, ( ⁇ , - ⁇ 2 ) 2 . If the solubility parameters are identical, the heat of mixing is zero and the dissolution/mixing process is driven by the entropy term T ⁇ S alone, and mixing will occur. If the solubility parameters are not identical, the term
  • solubility parameter is complicated by the presence of dipole and hydrogen bonding interactions.
  • dissolution may not be predictable by the single component, or dispersion solubility parameter, described above.
  • solubility is maximized when all the components for the solvent and material being dissolved are similar in polarity.
  • Two- or three-dimensional maps can be used to describe so-called solubility zones, areas, or spheres for such systems.
  • solubility parameter of a mixture of solvents is the sum of the solubility parameter of each component times the volume fraction of that component in the mixture.
  • Toluene for example, is known to be a good solvent for hydrocarbon material such as whole petroleum residua. This is probably because the solubility parameters of whole petroleum residua components lie within about ⁇ 2 (cal/cc) ' ⁇ of 8.9, or within 6.9 - 10.9 (cal/cc) '72 . Once thermal treatment of petroleum residua has begun, however, toluene fails to solvate the more polar components, which are formed as carbon deposition or coking ensues.
  • Separation schemes typically include steps such as precipitation of asphaltenes by a hydrocarbon solvent such as n-heptane and subsequent separation of the deasphaltened material (maltenes) by adsorption, ion exchange, size exclusion chromatography, or combinations thereof as disclosed by Schabron, J.F., G.W. Gardner, J.K. Hart, N.D. Niss, G. Miyake, and D.A. Netzel, The Characterization of Petroleum Residua, United States Department of Energy Report DE/MC/11076-3539 (1993), hereby incorporated by reference.
  • a hydrocarbon solvent such as n-heptane
  • the isolation of components from hydrocarbon materials, such as asphaltenes, can be based upon a solvent separation procedure based on the solubility difference between the precipitating solvent and the precipitated material.
  • the solubility (or lack thereof) of components of hydrocarbon materials can be dependent on both molecular weight and polarity considerations.
  • the solubility parameter of a particular hydrocarbon material or residuum fraction probably constitutes a range that is reflective of the variety of chemical components of the fraction.
  • the solubility parameter difference that results in a phase separation of two materials, such as asphaltenes in a solvent can be estimated using the Scatchard-Hildebrand equation, which involves several assumptions that take into account both the heat of mixing and entropy terms:
  • a a is the activity of the solute a
  • x a is the mole fraction solubility of a
  • M a is the molecular weight of a
  • p a is the density of a
  • N s is the volume fraction of solvent
  • ( ⁇ s - ⁇ a ) is the difference between the solubility parameters of the solute a and the solvent s.
  • solubility Assuming molecular weights of 750 and 1,500 g/mole for two hypothetical asphaltene molecules, the solubility as a function of the differences between solubility parameters of the asphaltene molecules and a range of solvent solubility parameters can be calculated.
  • solubility of an individual asphaltene molecule or complex decreases as the difference between solubility parameters increases. Also, a lower molecular weight molecule is more soluble than the higher molecular weight molecule for a particular difference in solubility parameter. From the above equations, it is apparent that the solubility depends both on molecular weight and polarity of the particular asphaltene molecule or associated specie. In an asphaltene mixture, for example, there exists a polarity and molecular weight continuum as described by Schabron, J.F. and J.G. Speight, The Solubility and Three-Dimensional Structure of Asphaltenes. Petroleum Science and Technology, 16 (3-4), pp. 361-376 (1998), hereby incorporated by reference.
  • solubility parameter of the solvent should be within about 1 (cal/cc) /2 of the solubility parameter of the polymer.
  • the difference in solubility parameters should be less than about 2 (cal/cc) ' ⁇ .
  • the difference in their solubility parameters should be less than about 7 (cal/cc) ' ⁇ .
  • an embodiment of the invention can be a molecular weight - polarity map developed specifically for hydrocarbon material components.
  • a molecular weight - polarity map can have a first axis having values relating to molecular weight. It may also have a second axis having values relating to solubility parameter.
  • a particular molecule or associated specie in a hydrocarbon material occupies a single point, or molecular weight - polarity coordinate location (3) on, on the map.
  • a mixture of molecules or mixture of molecules with associated species forming a continuum of polarity or apparent molecular weight values or a combination of both can be visualized as occupying a particular area on the map.
  • the solubility of a solute increases with decreasing polarity, decreasing apparent molecular weight, or a combination of the two.
  • the core material can comprise a variably adjustable core material having a molecular weight responsive to temperature change.
  • the core material may have polarity which is stabilized within a region of solubility even when the molecular weight may change.
  • a map can be used as a means of evaluating the characteristics of hydrocarbon materials or diagnosing processing conditions or the state of thermal degradation. It can also be used as a tool in efforts to diagnose and possibly intervene in the incipient precipitation of polar materials during hydrocarbon material processing.
  • phase diagram map can be developed by calculating the core material solubility regions, including the solubility region of asphaltenes, by determining solubility of core materials or asphaltenes in a variety of solvents.
  • solvents ranging from iso-octane, with a solubility parameter of 6.9 (cal/cc) ' ⁇ , to carbon disulfide, with a solubility parameter of about 10.0 (cal/cc) '/j .
  • the core material solubility region (1) can comprise between about 6.9 (cal/cc) ' ⁇ to about 11.0 (cal/cc) ' ⁇ .
  • the map can be based on solubility-parameter-tuned solvent mixtures providing even spacing between a plurality of solvent tuned contour lines (2) of about 0.5 (cal/cc) '/2 , except for the last series between toluene: CS 2 (55:45)(v:v) and CS 2 , where the spacing can be 0.6 (cal/cc) ' ⁇ .
  • the border between the soluble and insoluble regions is defined arbitrarily as the solubility of a mole fraction of 0.001 (0.1 %, or 1,000 ppm). This border is actually a point on a solubility gradient, where solubility increases towards the left-hand portion of a curve and decreases to the right.
  • a particular embodiment of the molecular weight -polarity map can be established by using a first solvent tuned contour line based on iso-octane, a second solvent contour line based on heptane, a third solvent tuned contour line based on heptane: toluene (2:l)(v:v), a fourth solvent tuned contour line based on heptane:toluene (1 :2)(v:v), a fifth solvent tuned contour line based on toluene, a sixth solvent tuned contour line based on toluene: carbon disulfide (55:45) (v:v), and an eighth solvent tuned contour line based on carbon disulfide.
  • the molecular weight - polarity related coordinate location (3)(for clarity not all the coordinate locations have leaders and identification numbers) of a particular material on the map was determined by three measurements.
  • a solubility or solvent spectrum of the material was obtained to determine between what lines on the map the material lies. This was accomplished by performing a series of solubility measurements in a series of solvents of increasing or decreasing solubility parameters and determining their weight percentages of the soluble material. Excess solvent to solute (40:1 v:w) ratios were used to minimize any potential effect of the solute on the overall solubility parameter of the system.
  • Stripper Bottoms - 371 °C (700 °F) These three stripper bottom represent a series of increasing severity of thermal treatment at atmospheric pressure for the same hydrocarbon material. In the sequence of increasingly severe treatment, the A bottoms were fed into the B unit, whose bottoms were fed into the C unit. These particular materials were allowed to remain in the strippers as they cooled down. Both Materials A and B were fully soluble in toluene, while Material C contained 13.5 weight percent toluene insoluble material, which yielded 17.9 weight percent ash.
  • the molecular weight - polarity map invention "peels" the layers of association with respect to a hydrocarbon material having unimodal characteristics.
  • the gravimetric data show the progression towards more polar species as the severity of thermal treatment increases.
  • Material C is generating both carbon or coke, or carbon or coke precursors (Fractions 6 and 7).
  • the data show that the number average molecular weights of the iso-octane- soluble maltenes are about the same for all three oils.
  • the molecular weight of each of the more polar fractions decreases significantly with thermal treatment.
  • the main difference between the various polar fractions for a particular material seems to be molecular weight.
  • the solubility parameters are similar for a particular series of polar materials with large differences in apparent molecular weight. This leads to the speculation that a residua colloidal system self-adjusts to lower the overall energy of the system by matching as closely as possible the polarity of the associated complexes to the solvent matrix (iso-octane maltenes).
  • the values are significantly lower than the number average molecular weight values determined by VPC.
  • the discrepancy cannot be wholly attributed to the use of polystyrene standards and the non-uniform response with refractive index detection from residua components of differing functionality. Some adsorption of materials on the polystyrene-divinylbenzene stationary phase may be occurring also.
  • the values determined by VPO represent the apparent number average molecular weights in 1 - 4 weight percent toluene solutions.
  • Figure 5 shows the results from injections of 100 uL of toluene solutions containing 0.3 - 15 mg onto the SEC column.
  • the retention volume decreased, indicating an increase in associations or apparent molecular weight.
  • the peak split into two peaks, suggesting the presence of significant associations.
  • This peak splitting and elution volume shortening phenomenon was not observed when a polystyrene standard with a molecular weight of 400 g/mole was injected under identical conditions. Thus, the peak splitting phenomenon is not likely due to overloading the column with sample.
  • the material eluted in about 3 mL of toluene.
  • the concentration at which significant complex formation begins for this asphaltenic material is estimated to be at the point where the peak splits. This occurs somewhere between 1.5 and 7.5 mg injected diluted into about 3 mL toluene elution solvent, which is between about 0.06 - 0.3 weight percent. This result may be consistent with the results of Andersen and Birdie, who reported a critical micelle concentration of asphaltenes in toluene near 0.38 weight percent using calorimetric titration. Andersen, S.I. and K.S. Birdi, Aggregation of Asphaltenes as Determined by Calorimetry, Journal of Colloid and Interface Science, 142, pp. 497-502 (1991).
  • the SEC number average molecular weights for a particular fraction generally decrease with increasing severity of thermal treatment.
  • the polydispersity Mw/Mn an indicator of molecular weight distribution, also decreases for a particular fraction with increasing severity of thermal treatment.
  • chromatograms appeared as essentially symmetrical peaks with one exception — the iso-octane maltenes (Fraction 1).
  • These chromatograms show a leading high molecular weight shoulder component (4) in the 273 °C (525 °F) material, which was smaller for the 343 °C (650 °F) material and was not evident for the 371 °C (700 °F) material.
  • this component of the iso-octane maltenes having an apparent high molecular weight appears to be related to at least one unimodal characteristic of hydrocarbon materials which can be destroyed with increasing severity of thermal treatment.
  • An embodiment of the invention based on this finding comprises an indicia of stability usc based upon the steps of detecting this unimodal characteristic stability component having apparent high molecular weight.
  • This approach may comprise providing a hydrocarbon material component analysis device, or devices in combination, which can be a size exclusion chromatography device as described above, or could also be other devices for identifying the apparent high molecular weight unimodal stability component such as a mass spectrometry device, an infrared spectrometry device, a raman spectroscopy device, gel phoresis device, paper chromatography device, or nuclear magnetic resonance device.
  • each hydrocarbon analysis device could be configured, as would be well known to those of skill in the art, so that the unimodal characteristic stability component could be identified.
  • the weight of residua or asphalt (W a ), the volume of toluene (V s ), and volume of iso-octane titrant (V t ) are recorded at the flocculation point where asphaltenes just begin to precipitate for each solution.
  • the flocculation ratio and dilution concentration are calculated as follows:
  • a plot of FR versus C can be made and the intercepts determined (FR- ⁇ .. and C mm ).
  • the Heithaus parameters are defined as follows:
  • FR is the volume fraction of toluene in a toluene- iso-octane mixture, assuming additive volumes.
  • the solubility parameter at FR-- a .. can be calculated.
  • FR,,...-. is thus a measure of the solubility parameter at infinite dilution at which asphaltenes begin to precipitate.
  • Such measurements also may have applicability in predicting precipitation of asphaltenes for mixtures of two or more residua.
  • a relatively larger FR max indicates a less soluble asphaltene.
  • solubility depends on both molecular weight and polarity, this can be due to a higher molecular weight or more polar asphaltene, or both.
  • C mm is the ratio of residua to titrant (iso-octane for this example although other solvents can be used) at which asphaltenes begin to precipitate.
  • a larger C m ⁇ n indicates a less compatible system (smaller P).
  • the solubility parameter at which asphaltenes begin to precipitate (at FR--, ax ) and the solubility parameters of the residua matrix (at C mm ) were calculated and are listed in Table 5 for the three stripper bottoms. Both the solubility parameter for the whole residua and the solubility parameter of the onset of asphaltene flocculation increase with increasing severity of thermal treatment.
  • the material that has been heated to the point of coke production is significantly more polar than the same material prior to coke production. This is also reflective of cracking and the removal of less polar distillates with heating.
  • an indicia of stability defined as p a /C m ⁇ n .
  • This indicia of stability pa/Cn - m can be based on the above described consideration that p a decreases and C m ⁇ n increases as the overall stability of the unimodal characteristics decreases.
  • a threshold of instability pa/Cmm value for can be assigned at a value within the range of about 0.1 to about 0.4.
  • the indicia of stability pa/Cmm for a particular hydrocarbon material can be compared to the threshold of instability pa/Cmm .
  • the p a /C m ⁇ n has decreased from a value of 0.87 to a value of 0.26.
  • the first value indicative of a relatively stable hydrocarbon material having unimodal characteristics while the second value suggests that the material has acquired some degree of multimodal character, which may include the formation of coke.
  • another embodiment of the invention can be an indicia of stability based upon determining the amount of precipitated asphaltenes which are soluble in a solvent having a polarity between that of the precipitating solvent and a solvent which can dissolve the precipitated asphaltenes completely.
  • asphaltenes were precipitated using heptane, although other precipitating solvents can be used including iso-octane, pentane, or hexane for example.
  • the precipitated asphaltenes can then extracted with a second solvent, in this example cyclohexane, having polarity that is between the precipitating solvent and a polarity which would substantially dissolve the precipitate completely.
  • Other solvents could be used as the second solvent depending on which solvent was used as the precipitating solvent such as pentane, heptane, or heptane: toluene 1 : 1 (v:v).
  • both hydrocarbon materials A and B are fully soluble in cyclohexane, yet the heptane asphaltenes are only partially soluble. Again, this is due to the associated unimodal nature of these materials.
  • the cyclohexane-soluble components of the asphaltenes can reflect the state of the solubilizing resins in these materials.
  • the disappearance of the cyclohexane-soluble portion of heptane asphaltenes as the stripper bottoms are increasingly heated is illustrated by the data for the stripper bottoms and appears to coincide with acquired multimodal characteristics, including coke formation. As such, an indicia of stability reflects an observed amount of precipitated asphaltenes soluble in the second solvent.
  • another embodiment of the invention can comprise an indicia of stability y/x be established by determining the weight percent asphaltenes soluble in the second solvent (Y) to the weight of the asphaltenes precipitated by the first solvent (X). A larger weight percent asphaltene would indicate a greater coking tendency, as would a smaller weight percent soluble portion of the asphaltenes.
  • a threshold of instability y/x can be assigned a value of between about 0.0 to about 1.0. The indicia of stability y/x can be compared to the threshold of instability y/x to determine the proximity of a hydrocarbon material to acquiring multimodal characteristics.
  • the ratio values for the three stripper bottoms are 1.2, 0.76, and 0.08 for the materials treated at 273, 343, and 371 °C (525, 650, and 700 °F), respectively.
  • the proximity of the hydrocarbon to acquiring multimodal characteristics, including coke formation, is closer as the value for this indicia of stability approaches zero.
  • unimodal character of hydrocarbon materials To further define aspects of the unimodal character of hydrocarbon materials, and illustrate the universal applicability of the above-described indica of stability, thresholds of instability, or their application to assessing proximity of the unimodal characteristics to acquisition of multimodal characteristics, including carbon deposition or coke formation, five additional hydrocarbon materials were evaluated.
  • These petroleum residua were Boscan, California Coastal, MaxCL, Redwater, B.C., and Vistar. While these particular residua were the focus of the following examples, their choice is not intended to limit the application of the described embodiments of the invention solely to such hydrocarbon materials.
  • Embodiments of the invention may have application over a broad range of hydrocarbon materials such as other petroleum residua, heavy oils, coal tars, shale oils, asphalts, or the like.
  • indicia of stability pa/Cmin and indicia of stability y/x from the cyclohexane soluble portions of precipitated asphaltenes for the five hydrocarbon materials are illustrated.
  • hydrocarbon materials were pyrolyzed at 400 °C for 60 and 90 minutes. Pyrolysis experiments were conducted in a sti ⁇ ed batch reactor system constructed from 4-inch diameter stainless steel pipe charged with about 120 g of hydrocarbon material. The reactor was heated to the desired set point temperature (400 °C) and held at that temperature for the duration of the experiment. At the end of the experiment, the reactor was allowed to cool and the contents of the reactor were recovered.
  • the carbon solids or coke can be separated from the product oil by solubility in toluene.
  • the amount of carbon solids formed at both 60 and 90 minute residence times was evaluated in terms of the above mentioned indica of stability. Heithaus titrations could not be performed on the 90 minute pyrolysis products because of sample instability and the immediate formation of precipitate in the titration cells. Therefore, the p a /C min embodiment of indica of instability was not determined for the 90 minute products.
  • indicia of stability y/x weight percent of precipitated asphltenes soluble in cyclohexane to asphaltenes soluble in heptane
  • indicia of stability y/x weight percent of precipitated asphltenes soluble in cyclohexane to asphaltenes soluble in heptane
  • y/x weight percent of precipitated asphltenes soluble in cyclohexane to asphaltenes soluble in heptane
  • K hydrocarbon solvation shell magnitude term
  • K K S • K F
  • K F hydrocarbon solvation shell magnitude term
  • K K S • K F
  • K F the amount of solvent adsorbed around a core material
  • K s asphaltene
  • K F solvated core materials
  • K values ranging from 3-6 at 25°C can be typical.
  • K As a hydrocarbon material is heated K decreases, indicating a decreasing amount of trapped solvent associated with the solvated core materials in the hydrocarbon material and flocculation of the core material may result. This may be a reversible process on cooling, unless pyrolysis reactions begin, at temperatures above 340 °C.
  • Solvation constants (K) are derived using:
  • K is the overall solvation constant for the hydrocarbon material
  • K s is the ratio of the size of the solvated core material to the size of the core material itself
  • K F is the amount of solvent otherwise associated with the solvated core materials
  • ⁇ a is the mass fraction of heptane asphaltenes, divided by an assumed density of 1.2 grams per cubic centimeter to yield the size fraction of the core materials
  • ⁇ rel is the relative viscosity.
  • core material precipitation with can be performed with a solvent such as heptane.
  • Zero shear viscosities are measured for a hydrocarbon material and for the co ⁇ esponding heptane maltenes ( ⁇ °, cps).
  • the ratio of ⁇ / ⁇ ° is called the relative viscosity ( ⁇ rel ) and is diagnostic of the manner in which core materials such as asphaltenes are suspended in a solution of maltenes. This value is somewhat dependent on the solvent used to precipitate the asphaltenes and is related to the state of peptization. A higher relative viscosity indicates a more significant unimodal characteristic.
  • the effective core material volume fraction, ⁇ eff is given by multiplying K by the volume fraction of heptane asphaltenes.
  • K s for a hydrocarbon material can indicate whether or not unimodal character is present.
  • the value of K s can depend on the experimental data used. For example, relative viscosities using heptane or iso-octane maltenes may vary somewhat. Results from the determination of K s using more than one approach, for a wide selection of hydrocarbon materials having unimodal characteristics, show that for unpyrolyzed hydrocarbon material such as petroleum residua the typical value of K s is 1.6. With pyrolysis (>340 °C), there is a carbon deposition or coke induction period during which a multimodal system begins to form as discussed by Schabron, J.F., A.T. Pauli, and J.F.
  • a hydrocarbon material may have sufficient association between components to manifest unimodal characteristics such as a size ratio of the core material to the solvated core material (K s ) when K s has a value equal to or greater than about 1.1, or a size ratio of a plurality of solvated core materials to other associated solvent (K F ) when K F has a value equal to or greater than about 1.4, or a sufficient solvation shell (K) when K has a value equal to or greater than about 1.5.
  • K s size ratio of the core material to the solvated core material
  • K F a size ratio of a plurality of solvated core materials to other associated solvent
  • K F a sufficient solvation shell
  • K s , K F , and K for a particular hydrocarbon material may be as indicia of stability for the unimodal characteristics of a hydrocarbon material.
  • a first indicia of stability may comprise determining an average size ratio of the solvated core material to the core material itself (indicia of stability Ks ), or determining an average size ratio of associated solvent around a plurality of solvated core materials to the core material itself (indicia of stability KF ), or determining a size ratio of the associated solvent and solvation shell to the core material itself (indicia of stability ⁇ ).
  • these size ratios may be determined using a variety of instruments such as a nuclear magnetic resonance spectroscopy device, a nuclear magnetic resonance tomography device, a mass spectrometry device, an infrared spectrometry device, a microscope device, a raman spectroscopy device, a size exclusion chromatography device, a gel electrophoresis device, or a paper chromatography device.
  • the size ratios may be determined prior to processing of the hydrocarbon material or during processing of the hydrocarbon material. For example, nuclear magnetic resonance imaging has shown that at least two distinct phases are present after pyrolysis with subsequent coke formation.
  • establishing a threshold of instability for unimodal characteristics of hydrocarbon materials may comprise assigning a threshold of instability to size ratios having a value of K s at about 1.1, or K F at about 1.4, or K at about 1.5. Below these values the level of association between components in a hydrocarbon material may be insufficient to exhibit unimodal character and transition to multimodal character may be initiated including heterogenous mixture formation, carbon deposition, or coke formation.
  • various embodiments of the invention allow for comparison of determined indicia of stability to the determined thresholds of instability with respect to K s , K F , or K so that the proximity of a particular hydrocarbon material to formation of multimodal characteristics.
  • This may comprise comparing the value of K s for a given hydrocarbon material to the threshold of instability value of K s .
  • the value of K F for a given hydrocarbon material to the threshold of instability value of K F or the value of K for a given hydrocarbon material to the threshold of instability value of K.
  • Another embodiment of the invention can be based upon the free solvent volume of the hydrocarbon material.
  • the free solvent volume of hydrocarbon materials having unimodal character relates to the fraction of the total solvent that is not associated with the core materials or associated with or trapped by a plurality of solvated core materials.
  • This indicia of stability can co ⁇ elate with the amount of initial carbonaceous deposition, including coke formation, below pyrolysis temperatures or the initial amount of carbonaceous deposition formed in the early stages of a pyrolytic process.
  • This indicia of stability does not include the amount of carbonaceous deposition when pyrolysis is carried to completion.
  • the total amount of carbonaceous deposition, including deposition of coke may be estimated by further determining the hydrogen-carbon ratio of the hydrocarbon material. This ratio is subsequently used to calculate the weight of the total carbon content of an amount of hydrocarbon material as would be well known to those with skill in the art.
  • the average K s for unpyrolyzed hydrocarbon material value can be about 1.6.
  • Values for ⁇ FS co ⁇ elate to deposition of carbonaceous material when the value for K s is held constant.
  • Other methods of determining free solvent volume, or modifying the values relating structure consideration such as H/C ratio, or fraction of bridge head aromatic carbons may be used, and are encompassed by the invention.
  • the weight percent heptane asphaltenes ( ⁇ a ), and the value of petizabiltiy of asphaltenes (p a ) may be determined as discussed above. Keeping in mind that the concept can work with other precipitating solvents and other dissolvents as discussed.
  • the five hydrocarbon materials were pyrolyzed in five (5) gram reactor tubes at 400° C for 90 minutes.
  • the initial amount of carbonaceous deposition, including coke deposition, is set out for each hydrocarbon material in Table 11.
  • Figure 13 is a plot of initial deposition of carbonaceous material versus ⁇ FS .
  • ⁇ FS decreases the amount of initial carbonaceous material that forms increases for a given set of processing parameters.
  • an embodiment of the invention provides an indica of stability based upon ⁇ FS with respect to predicting the amount of initial carbonaceous deposition.
  • plots of initial carbonaceous material formation versus ⁇ FS could be generated for any variety of hydrocarbon materials for particular processing conditions, such as different pyrolysis temperatures or for different pyrolysis times or in various combinations, to rank the hydrocarbon materials in terms of relative carbon deposition potential based upon ⁇ FS .
  • additional embodiments of the invention may include selecting distillation parameters to distill hydrocarbon material having unimodal characteristics use predetermined indicia of stability to avoid reaching the threshold of instability.
  • selecting distillation parameters to distill hydrocarbon material having unimodal characteristics use predetermined indicia of stability to avoid reaching the threshold of instability.
  • a method of processing hydrocarbon material using distillation parameters based upon indicia of stability, indicia of instability, independently or in cooperation may allow distillation of hydrocarbon materials so as to have ascertainable indicia of stability in closer proximity to the threshold of instability compared to typical distillation parameters.
  • the output of liquid distillables per unit amount of said hydrocarbon material may be increased by comparison with typical parameters of distillation.
  • an increase in the amount of liquid distillables from the same amount of hydrocarbon material may decrease the amount of energy used per unit of liquid distillate produced, or may also reduce the amount of emissions generated per unit of liquid distillate produced. Such reduction in emissions may be a reduction in carbon dioxide.
  • hydrocarbon materials when distilled in a continuous distillation event it may increase the purity of at least a portion of said liquid distillates.
  • Another embodiment of the invention understandably includes, the selection of hydrocarbon materials for purchase or processing based upon determined indica of stability for the degree of unimodal characteristics.
  • some hydrocarbon materials which have indicia of stability which show a high level of unimodal characteristics may have greater desirability for some parameters of processing.
  • selecting distillation parameters for hydrocarbon material having unimodal characteristics may designed to reach a predetermined level of instability characteristics. As such, distilling these hydrocarbon materials using such distillation parameters may continue until reaching said predetermined level of instability characteristics.
  • a method of processing hydrocarbon material in this fashion initiate the formation of a predetermined amount of carbon or coke. Again as above, such distillation parameters may allow for maintaining continuous distillation until reaching the predetermined level of instability characteristics.
  • an embodiment of the invention comprises the isolation of these higher purity products.
  • this invention can be embodied in a variety of ways.
  • each of the various elements of the invention and claims may also be achieved in a variety of manners.
  • This disclosure should be understood to encompass each such variation, be it a variation of an embodiment of any apparatus embodiment, a method or process embodiment, or even merely a variation of any element of these.
  • the words for each element may be expressed by equivalent apparatus terms or method terms — even if only the function or result is the same.
  • Such equivalent, broader, or even more generic terms should be considered to be encompassed in the description of each element or action. Such terms can be substituted where desired to make explicit the implicitly broad coverage to which this invention is entitled.
  • the applicant should be understood to claim at least: i) a molecular weight / polarity map system; ii) each of the coking indexes; iii) a system of pre-distillation evaluation of hydrocarbon material; iv) a nearly continuous distillation system; v) a system for optimizing the yields of distillable liquids; vi) a system for determining the coking indexes; vii) the resulting products; viii) the related methods disclosed and described, ix) similar, equivalent, and even implicit variations of each of these devices and methods; x) those alternative designs which accomplish each of the functions shown as are disclosed and described; xi) those alternative designs and methods which accomplish each of the functions shown as are implicit to accomplish that which is disclosed and described; xii) each feature, component, device, and step shown as separate and independent inventions; xiii) the combinations of applied systems including the designs disclosed, xiv) the resulting products produced by such systems or components, xv) related methods including the

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Abstract

Cette invention concerne une matrice poids moléculaire-polarité avec des lignes de réponse (2) fonction de différents solvants qui matérialisent une région de solubilité du matériau dans laquelle s'inscrivent les emplacements coordonnés (3), en termes de poids moléculaire-polarité, de composants de matériaux hydrocarbonés. Certaines caractéristiques unimodales fournissent des indices vérifiables de stabilité ou des seuils d'instabilité permettant de définir, pour des caractéristiques unimodales en rapport avec des matériaux hydrocarbonés, la proximité de caractéristiques multimodales. Cette invention permet de savoir si de tels matériaux hydrocarbonés conviennent pour divers types de méthodologies de traitement, ou bien de déterminer des paramètres de traitement soit avant, soit pendant le traitement. Par rapport à des techniques de traitement classiques, les prévisions de proximité relatives à la formation de caractéristiques multimodales peuvent permettre d'établir des caractéristiques de traitement en continu, d'accroître les rendements, de réduire la consommation d'énergie ou l'importance des émission par unité de matériau hydrocarboné de ce type. Les produits unimodaux produits ou traités au moyen de cette technologie peuvent également présenter un degré de pureté plus poussé.
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EP00941317A EP1198714A4 (fr) 1999-06-10 2000-06-09 Technique de prevision d'un etat proche de la cokefaction
AU56036/00A AU776038B2 (en) 1999-06-10 2000-06-09 Predicting proximity to coke formation
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WO2000077120A9 (fr) 2001-11-08
EP1198714A2 (fr) 2002-04-24
CA2371790A1 (fr) 2000-12-21
AU776038B2 (en) 2004-08-26
CA2371790C (fr) 2011-10-04
WO2000077120A3 (fr) 2001-10-04
AU5603600A (en) 2001-01-02
EP1198714A4 (fr) 2003-07-09
MXPA01012580A (es) 2003-08-01

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