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WO2000071494A1 - Procede d'amelioration de la valeur des ressources naturelles d'hydrocarbures - Google Patents

Procede d'amelioration de la valeur des ressources naturelles d'hydrocarbures Download PDF

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Publication number
WO2000071494A1
WO2000071494A1 PCT/US2000/014128 US0014128W WO0071494A1 WO 2000071494 A1 WO2000071494 A1 WO 2000071494A1 US 0014128 W US0014128 W US 0014128W WO 0071494 A1 WO0071494 A1 WO 0071494A1
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Prior art keywords
heteroatom
containing compounds
extract
fraction
solvent
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English (en)
Inventor
James W. Bunger
Donald E. Cogswell
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James W Bunger and Associates Inc
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James W Bunger and Associates Inc
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Priority to EEP200100622A priority Critical patent/EE04818B1/xx
Priority to US09/979,702 priority patent/US6875341B1/en
Priority to AU48592/00A priority patent/AU4859200A/en
Publication of WO2000071494A1 publication Critical patent/WO2000071494A1/fr
Anticipated expiration legal-status Critical
Priority to US11/098,882 priority patent/US7857965B2/en
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • 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
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only

Definitions

  • This invention relates to treatment of kerogen oil and other hydrocarbonaceous natural resources.
  • Kerogen oil is derived from kerogen, the solid hydrocarbon contained in oil shale rock.
  • Oil shale is a hydrocarbon bearing rock that occurs in various places in the world (Kirk-Othmer Concise Encyclopedia of Chemical Technology, Wiley-rnterscience, 1985 p 811).
  • Kerogen oil is a liquid product recovered from oil shale through a pyro lysis reaction using thermal retorts. The liquid product so produced is also referred to as raw shale oil or simply shale oil.
  • Kerogen oil may be high in nitrogen content when recovered from Green River Formation oil shale (U.S.A.), high in oxygen content when recovered from Kukersite oil shale (Estonia) or may contain other combinations of heteroatoms.
  • heteroatom compounds were extracted and used for their unique chemical values the economics of non-conventional hydrocarbonaceous natural resource production may be dramatically improved.
  • extract as an asphalt is likewise not shown by a practical example.
  • the extract from a raw shale oil would be by itself too low in viscosity to be an effective asphalt binder.
  • Oil shale does not contain the high boiling constituents (>530°C) that are present in petroleum from which conventional asphalts are made and which are the compounds primarily responsible for the semi-solid rheologic properties required for a specification asphalt.
  • Che discloses the desirability of high selectivity, but fails to define what is meant by selectivity.
  • the specification cites the desirability of first distilling the shale oil into a lighter fraction and heavier fraction and separately processing these fractions.
  • Selectivity is achieved by "Dividing the shale oil into fractions according to boiling point, which generally divides the shale oil into fractions according to molecular weight. This reduces the competing solubilization of lighter non-nitrogen- containing compounds with the result and effect that heavier nitrogen-containing compounds compete only with heavier non-nitrogen-containing compounds.
  • Che does not disclose a practical means of solvent recovery nor uses for extracted nitrogen components.
  • the nitrogen (heteroatom-containing) compounds in shale oil are materials that are to be removed, i.e., substances regarded as objectionable and of little worth, and that are to be destroyed or discarded. If any value is derived from the nitrogen materials, it is only incidental to the main object of increasing the value of the shale oil for purposes of refining by removing the nitrogen compounds. Consequently, the nitrogen-containing extracts have generally been viewed as low- or no- value products.
  • an object of the invention to provide a process that will extract and convert compounds contained in oil from hydrocarbonaceous natural resources to produce products that are more valuable to the marketplace than products made from a traditional petroleum refinery.
  • An embodiment of the invention is a process wherein hydrocarbonaceous oil, which is a mixture of organic compounds comprising primarily C, H, N, S and O, is treated in a liquid-liquid extraction process with a selected polar solvent to extract heteroatom-containing compounds from non-heteroatom-containing compounds with a high coefficient-of-separation (COS).
  • the heteroatom-containing compounds recovered from the polar solvent are then used directly as a valuable specialty or commodity products or they are fed to an upgrading processes where they may be fractionated, derivatized or subjected to a dealkylation environment and otherwise processed to manufacture speciality or commodity products.
  • the dealkylation process reduces the molecular weight of the heteroatom-containing molecule by cracking off non-heteroatom-containing side chains and saturated ring systems from the aromatic and resonance-stabilized ring systems.
  • the product is a concentrate of valuable heteroatom-containing materials, which are materials originally in the hydrocarbonaceous oil and derived from higher molecular weight heteroatom materials that have been freed or dealkylated of non-heteroatom-containing side chains and saturated ring systems.
  • the dealkylated heteroatom-containing molecules which are comprised largely aromatic or unsaturated ring systems and which contain heteroatoms within or directly bonded to the ring system, are then recovered, concentrated and further processed to produce marketable products.
  • the non- heteroatom-containing compounds obtained from the extraction along with non- heteroatom-containing alkyl groups produced in a dealkylation process and recovered with the raffinate in the extraction process are processed for petroleum products, such processing being greatly simplified by the prior removal of a large portion of the heteroatom-containing compounds.
  • Green River Formation kerogen oil is first extracted by a polar solvent applied in proportions of approximately 0.5- 2.0: 1.0 to generate a polar extract and a non-polar raffinate. Solvent is recovered by distillation for reuse by the practice of the invention.
  • the polar extract may be used directly as a commodity such as an antistripping agent in asphalt blends, as a dispersant for marginally compatible process streams or for other applications for broad-range concentrates, or it may be processes for more refined, specification products.
  • the polar extract is distilled to separate the extract into light, middle and heavy molecular weight fractions.
  • the middle distillate stream may be sent to a cracking unit where alkyl groups are removed from heteroatom-containing ring systems.
  • the product from the cracking unit may be returned to the extraction unit where the dealkylated heteroatom-containing rings are separated from the non-heteroatom-containing alkyl groups.
  • the dealkylated heteroatom-containing rings are recovered in the light distillate stream along with the lower molecular weight heteroatom-containing molecules originally in the kerogen oil.
  • the light distillate may be sent to a more severe thermal hydrodealkylation unit (Figure 2) to remove remaining methyl groups where the products may be purified ( Figure 3) to pure compounds.
  • a drag stream may be drawn from the hot receiver in the cracking unit to prevent buildup of heavy non-reacting substances in the system.
  • the heavy distillate from the distillation of the polar extract and material recovered in the drag stream from the cracking unit may be used directly as an antistripping agent in asphalt blends or as a dispersant for marginally compatible process streams or an asphalt additive or for other uses as specified below.
  • the non-polar raffinate may be sent directly to a petroleum refinery or sent to a catalytic hydrotreating unit for reduction of nitrogen and sulfur, making this material directly amenable to petroleum refining or for other uses as specified below.
  • An advantage of the present invention is that the raffinate and extract process streams can each be processed economically into products, with little or no "waste" streams that have little or no value in market. This is because the molecular compounds that contain the heteroatoms are concentrated in the extract, substantially free of non-heteroatom-containing compounds, and conversely, the non-heteroatom- containing compounds are concentrated in the raffinate, substantially free of heteroatom-containing compounds.
  • the process of the invention can be operated to produce more of the broad-range concentrate that is not as limited by end-use consumption, without having to reduce total process throughput, which would result in adverse economic consequences.
  • Such a flexibility is not possible with prior-art system, where low value, or unmarketable waste streams must be processed and disposed of.
  • any so-called by-product streams are usually produced at costs above the market value, which requires that the more valuable product streams subsidize the lower value streams in order to make the process profitable.
  • the process must produce a maximum amount of high- value product, or it is not viable.
  • the margin for the high- value product is lower, because revenue is required to offset the cost of the by-product production.
  • the composition of the heteroatom-containing extract stream in the present invention is such that expensive processing is not required to form an economically viable product from the extract.
  • the solvent system in the extraction is not used in an excessive volume, and is in a chemical form that is relatively inexpensive to remove from the extract and recycled.
  • the extract can then be further processed for production of high- value products, such as pyridine or resorcinol, or used essentially as-is for products of intermediate value, but which in the market can be produced at a higher volume, such as an asphalt or crude oil additive.
  • the process of the invention can be adjusted to maximize the production of a processed high- value product, or to a direct, intermediate value, but higher volume product; in the event the market for the high- value material becomes saturated.
  • the ability to produce a processed, high- value product and a direct, unprocessed product simultaneously also allows the practitioner to build a plant that is much larger than would be justified if only the high- value product was being produced. This permits exploitation of the economies of scale, without which a process for the high-value product would be uneconomical.
  • a discovery related to the present invention is that a large portion of the heteroatom molecules in hydrocarbonaceous resources are chemically related to valuable heteroatom feedstocks, such as pyridine and picoline.
  • pyridine-type chemical structures have not been evident in abundance by typical prior-art chemical analysis of Green River Formation kerogen oil, but it has been found by the applicants that such chemical structures do exist in significant amounts, but combined with side chains. By removing the side chains, which are mostly alkyl in nature, certain valuable heteroatom compounds can be produced.
  • side chains which are mostly alkyl in nature
  • the heteroatom portion of carbonaceous oils was regarded as something to be destroyed or removed and discarded as something of little worth.
  • the discovery of the chemical nature of the carbonaceous oil has lead to an economical process wherein both the non-heteroatom and heteroatom constituents are economically exploited.
  • the recognition of the chemical structure of the heteroatoms has also led to the recognition that these compounds have value directly as-is, without processing to remove the side-chains. Accordingly, the heteroatom mixture of the extract has been found valuable for such uses as asphalt additives, and other uses which are further enumerated herein.
  • heteroatom extract can be used as-is for products with a relatively high market volume, or can be processed to compounds with a high- value but with a limited market volume, has led to the invention of the present process wherein it is possible to adapt the process toward either a direct extract product or a processed extract, depending upon market conditions. For example, if the market for the high- value, low- volume process product becomes saturated or the price becomes depressed, production can be directed to the intermediate value high-market volume material. This ensures that the capacity of the plant will always be utilized, and that a profitable product can be made, regardless of market conditions.
  • Figure 1 is a block diagram of a preferred process of the invention.
  • Figure 2 is a block diagram of a dealkylation process of the invention.
  • Figure 3 is a block diagram of a purification process of the invention.
  • Figure 4 is a block diagram of a solvent recovery process of the invention.
  • Figure 5 is a block diagram of a hydropyrolysis process of the invention.
  • Figure 6 is a block diagram of an alternate process of the invention.
  • Figure 7 is a block diagram of a second alternate process of the invention.
  • Oils for treatment by the invention are those derived by extraction or heat treatment of carbonaceous materials, e.g., oil shale, oil sands, tar sands, coal, gilsonite or biomass.
  • Oil shale consists of a marlstone-type sedimentary inorganic material that contains complex organic polymers that are high molecular weight solids.
  • the organic kerogen is a three-dimensional polymer, insoluble in conventional organic solvents, and associated with small amounts of a benzene-soluble organic material, bitumen ...Oil shale deposits occur widely throughout the world [and] the geology and the composition of inorganic and organic components of oils shale varies with deposit location.” Kirk-Othmer, Concise Encyclopedia of Technology, 1985 (John Wiley & Sons). Oil sands, also known as tar sands or bituminous sands, are sand deposits impregnated with dense, viscous petroleum.
  • Trosand is any consolidated or unconsolidated rock (other than coal, oil shale or gilsonite) that either: (1) contains a hydrocarbonaceous material with a gas-free viscosity, at original reservoir temperature, greater than 10,000 centipoise; or (2) contains a hydrocarbonaceous material and is produced by mining or quarrying.
  • coal is a dark burnable solid, usually layered, that resulted from the accumulation and burial of partially decayed plant matter over earlier geologic ages. Kirk Othmer Concise Encyclopedia of Chemical Technology, 1985 (John Wiley and Sons). Further, “the formation of coal, the variation in its composition, its microstructure and its chemical reactions indicate that coal is a mixture of compounds.”
  • “Gilsonite” is a natural hydrocarbon substance classed as one of the asphaltites. Asphaltites are asphalt-like substances characterized by their high softening point (above 110 °C)." Kirk-Othmer, op. Cit. p 559.
  • Biomass is a renewable biological material, as agricultural or forestry waste or energy crops, used for the production of energy. Grant andhackh's Chemical Dictionary, 5 th Ed., McGraw Hill (1987). With each of the above-described natural resources, the oil derived from them is comprised of a mixture of compounds, some of which contain no heteroatoms and are desirable for refining to petroleum products, and others of which contain heteroatoms and are undesirable for refining to petroleum products. In each case it is the objective of the invention to selectively recover those components which are undesirable for refining to petroleum products, to concentrate these components and to produce chemical or commodity products, other than direct petroleum products such as fuels and lubricants, that command value in the marketplace.
  • Oil Pretreatment Depending upon the method of producing the oil it may be desirable but not necessarily a requirement to pretreat the oil for removal of solids, insolubles, salts or other heterogeneous (mixed phase) substances. Such removal may be made by any convenient means such as filtration, centrifugation, settling, washing, decanting and the like.
  • the oil may be prefractionated by distillation.
  • Such fractionation may consist solely of removing lower boiling components or it may include fractionation of one or more distillate fractions for independent processing. It is intended that any such pretreatment steps may be effected without departing from the spirit of the invention.
  • Any suitable liquid-liquid extraction apparatus may be used, preferably operated in a counter-current continuous mode.
  • the solvent system comprises a major portion of a polar solvent and a minor portion of water.
  • the polar solvent is selected and introduced in such a manner and in proportions that a separate phase is formed with the oil.
  • Suitable polar extraction solvents include those that form a separate phase from the non-polar constituents of the oil, including, but not limited to, formaldehyde, formic acid, methanol, acetaldehyde, acetic acid, ethanol, propanol, isopropyl alcohol, furfural, phenol, sulfolane, N-methyl-2-pyrrolidone, or combinations of the above.
  • Other solvents may include aldehydes, ketones, ethers, esters, amides, and amines which are generally comprised of 10 carbons or less.
  • a minor portion of water is present in the solvent system to act as an antisolvent.
  • the antisolvent action of water decreases the solubility of heteroatom-containing compounds in the raffinate.
  • solubility of the polar solvent system in the raffinate is decreased, which increases partitioning of heteroatom-containing compounds into the extract.
  • the non- heteroatom-containing compounds are also directed to the raffinate by the presence of water, because water inhibits the solubility of non-heteroatom-containing compounds in the extract.
  • water in the solvent system tends to reject solvent and heteroatom-containing compounds from the raffinate, and reject non-heteroatom- containing compounds from the extract.
  • a light non-polar solvent may optionally be introduced in such a manner and in such a proportion to enhance the separation of phases when contacting the selected polar solvent with the oil.
  • Suitable non-polar solvents include, but are not limited to, the lower normal paraffins such as n-propane, n-butane, n-pentane, n- hexane or n-heptane, and isoparaffins and cycloparaffins that are comprised generally of no greater than 7 carbons. It is contemplated that a non-polar solvent, if desired, would be used simultaneously with a selected polar solvent to achieve the objects of the invention.
  • the countercurrent extraction step may be preceded by one or more single- stage extraction steps or by presaturating the oil with either a polar solvent or a non- polar solvent, or both, as required to achieve the objects of the invention, so long as the total amount of solvent contacted does not exceed the maximum desirable amount as specified in its relationship to the amount of oil.
  • the temperature (and pressure, if needed to achieve a desired temperature) of the extraction system may be varied to enhance the desired results.
  • the selection of the solvent system, the method of contacting, the solvent/oil ratio, the throughput rate, the contact temperature and other process variables are selected so as to achieve the following objectives.
  • a coefficient of separation is defined as:
  • the COS may be applied in any convenient fashion to describe the degree to which the separation objectives have been achieved.
  • a perfect separation would be one in which all of the nitrogen- containing compounds would be recovered in the extract and none of the non- nitrogen-containing compounds would be recovered in the extract.
  • the COS is calculated by measuring by any convenient means the concentration of both the desirable components and the undesirable components in the feedstock and in either the extract or the raffinate and applying the mathematical treatment described above.
  • the maximum COS is achieved by varying the selection of solvent, the concentration of water, the temperature, the solvent-to-oil ratio, the number of extraction stages, the throughput rate and other process variables. In the practice of the invention it is the object of the invention to maximize the COS, consistent with the other objectives of the invention.
  • the COS is measured for the heteroatom compounds appropriate for the hydrocarbonaceous oil being extracted. For a kerogen oil derived from Green River Formation oil shale, the heteroatom content is principally nitrogen, and measurement of the COS for nitrogen-containing compounds will effectively measure the separation of heteroatom compounds.
  • the heteroatom content is principally oxygen, so measurement of the COS for oxygen- containing compounds would effectively measure the separation of heteroatom compounds.
  • separation of the heteroatom compounds can be measured by a COS of oxygen-containing compounds, or nitrogen-containing compounds, or a combination thereof, depending upon the heteroatom content of the hydrocarbonaceous oil. It is understood, that where, for example, a COS for extraction of nitrogen-containing or oxygen-containing oils is mentioned, the same teachings apply to other hydrocarbonaceous oils with different heteroatom contents. Further, the invention applies to heteroatom compounds other than those of nitrogen and oxygen, where the oil is of appropriate composition.
  • the COS may also be applied to specific compound-types, e.g. pyridines, if these types are the desired components
  • a kerogen oil derived from Green River Formation (U.S.A.) oil shale possessing 1.8% nitrogen and exhibiting an average molecular weight of 325 Dalton is added to a separatory funnel containing an equal weight of a selected solvent system comprised of 80% formic acid and 20% water.
  • the temperature of the system is elevated to 40°C to ensure no crystallization of waxes that are contained in the kerogen oil.
  • the mixture is vigorously shaken until partitioning between the liquid phases is at equilibrium.
  • the extract layer is first drawn from the bottom of the separatory funnel and kept separately from the top layer, or raffinate, which is successively drawn from the separatory funnel.
  • the extract comprising 37% of the feed, exhibits a nitrogen content of 4.0%).
  • the raffinate comprising 63% of the feed, exhibits a nitrogen content of 0.51%.
  • the coefficient-of-separation for this extraction assuming one nitrogen atom per nitrogen-containing molecule, is 11.1% and is calculated as follows:
  • polar solvent is made based on selectivity, ease of recovery, low reactivity and low cost.
  • Selectivity is defined in terms of COS.
  • Ease of recovery considers both recovery efficiency, defined as the percentage of solvent recovered per pass, and other handling characteristics such as low toxicity or corrosivity.
  • Low reactivity is defined as exhibiting negligible chemical effects on the composition of the extract. Low cost implies that the solvent should not be difficult to synthesize. In general, small molecules possessing dipole moments of greater than 1.0
  • Debyes are candidates for the selected polar solvent. Chlorinated or halogenated solvents are to be avoided, both because of the additional environmental hazards and the adverse effects the presence of halogens have on downstream processing. Other undesirable solvents are oxidizing solvents, reducing solvents, mineral acids and solvents that promote free radical or ionic polymerization reactions.
  • N-methyl-2-pyrrolidone >1.00 est.
  • non-polar co-solvent Selection of a non-polar co-solvent is made based on selectivity, ease of recovery, low reactivity and low cost, as defined above.
  • the non-polar co- solvent serves to enhance the antisolvent effect of water.
  • non-polar solvents In general, small molecules possessing a dipole moment of less than 0J Debyes are candidates for selection as non-polar solvents.
  • Aromatic hydrocarbons are to be avoided because of their adverse effects on selectivity and olefins are to be avoided because of their instability and reactivity.
  • Chlorinated or halogenated solvents are to be avoided because of their adverse effects on selectivity and undesirable environmental effects.
  • Suitable non-polar solvents include, but are not limited to normal paraffins, isoparaffins, and cycloparaffins with less than 7 carbon atoms.
  • Examples, all of which exhibit dipole moments (in debyes) less than 0J, are: n-propane n-butane n-pentane n-hexane n-heptane cyclopentane methylcyclopentane cyclohexane methylcyclohexane
  • water as an anti-solvent in conjunction with a polar organic solvent and not as a principal extraction solvent is an important aspect of the invention.
  • the addition of a non-polar solvent is optional to enhance the anti-solvent effects of water.
  • a non-polar solvent As an example of the addition of a non-polar solvent., a 200-550 °C distillate of Kukersite kerogen oil was vigorously shaken with 1.5 parts of polar solvent, comprised of 90%> formic acid and 10% water, and 1.0 parts non-polar solvent, comprised of n-hexane (all parts by weight) and allowed to settle until 2 phases were formed. The bottom extract phase was separated from the top raffinate phase and the solvent was separately removed from each phase by distillation according to the practice of the invention.
  • the extract amounted to 19%) of the total distillate and raffinate amounted to 81%) of the total distillate.
  • the extract and raffinate were separately analyzed by a gas chromatograph equipped with a mass selective detector (GC-MSD) in a total ion current (TIC) mode.
  • GC-MSD mass selective detector
  • TIC total ion current
  • COS is broad and can be applied to any two compositional characteristics for which analytical information is available, and that such application is not restricted to the general class of heteroatom-containing compounds but may be applied to specific heteroatom- containing compounds or specific non-heteroatom-containing compounds to achieve the objectives of the invention.
  • This amount of solvent is the least amount that can be used in practice and will depend on the nature and composition of the oil, the structure of the solvent, the presence of other solvents, the temperature and the configuration of the extraction system. In practice, it may be desirable to use more than the minimum amount of solvent required to induce two phases, if by increasing the solvent-to-oil ratio the COS is increased correspondingly. In all practical systems it is expected that there will be a limit to the maximum amount of solvent that can be introduced to a fixed amount of oil before the COS will no longer rise and will begin to fall.
  • the desired amount of solvent will be between the limits of the minimum amount required to create two phases and the amount required to maximize the COS.
  • the selection of solvent and the temperature of extraction are chosen to maximize the COS while minimizing the solvent-to-oil ratio.
  • Table IV shows the effect of solvent-to-oil ratio on extraction of a kerogen oil distillate.
  • an object is to increase the separability of the nitrogen and non-nitrogen compounds, as measured by the COS. In this way, the combined value of the raffinate and extract fractions is optimized, rather than optimizing one fraction while seriously devaluing the other. In addition, this increase in value is achieved by a significant saving in solvent, as compared to typical prior-art practice.
  • Figure 4 shows a diagram of a preferred solvent recovery scheme for the selected solvent of formic acid and water.
  • extract and raffinate are sent to separate distillation apparatus where they are heated to distill the solvent.
  • Formic acid forms an azeotrope with cyclic hydrocarbons and the boiling point of this azeotrope is lower than the boiling point of either formic acid or water.
  • water forms an azeotrope with certain light aromatics typically found in hydrocarbonaceous oils.
  • solvent recovery is aided by the azeotropic distillation of components naturally occurring in the oil.
  • these azeotropic distillates disengage into separate liquid phases, a low density, upper hydrocarbon phase and a high-density solvent phase.
  • the light hydrocarbon phase can be recycled to the distillation apparatus to further assist the stripping of the solvent, reintroduced to the feed system to assist extraction selectivity, or withdrawn as product.
  • hydrocarbonaceous oil is charged to one end of a countercurrent continuous extraction unit.
  • Polar solvent is simultaneously introduced to the opposite end of the extraction unit.
  • the choice of which end to introduce each stream will depend upon consideration of relative densities.
  • the oil and the polar solvent are pumped to the system in proportions designed to maximize the COS while minimizing the solvent-to-oil ratio while the raffinate and the extract are withdrawn from the system in proportions to match their relative yields. Temperature is controlled at a predetermined level.
  • the extract and the raffinate are taken to separate units wherein the solvents are recovered from each stream and the solvent is recycled to the extraction unit.
  • Fresh (makeup) solvent may be added to supplement process losses occurring through small amounts of solvent remaining in the extract or raffinate, or solvent may be removed (e.g., by a drag stream) to maintain quality of solvent.
  • the extract and raffinate are subsequently used directly or are further processed to enhance their value.
  • a kerogen oil derived from Green River Formation oil shale and containing high concentrations of nitrogen-containing compounds is pumped to the bottom of a column while a mixture comprised predominantly of a carboxylic acid with lesser amounts of water is pumped to the top of the column.
  • the choice of solvent is formic acid and water with formic acid being the major component, generally greater than 70%> and water being the minor component, generally less than 30%>.
  • the oil may be presaturated with extraction solvent prior to pumping to the bottom of the column in order to accelerate the phase separation upon contact with the extraction solvent.
  • the temperature and solvent-to-oil flow ratio is selected so as to maximize the
  • the selected solvent- to-oil ratio is less than 2 but greater than 0.5 with a typical ratio of about 1.
  • the temperature of the column is controlled by any convenient means, generally between 20°C and 120°C, but typically between 40°C and 90°C.
  • the selected solvent system and the oil presaturated with the selected solvent system are continuously pumped in a countercurrent fashion where the two phases are allowed to contact each other by droplets of the discontinuous phase dispersed in the continuous phase. At the interface of these separate phases the non-heteroatom- containing compounds tend to partition to the raffinate phase while the heteroatom- containing compounds tend to partition to the extract phase.
  • the extent to which this partitioning occurs depends upon the effectiveness of the contact system, the ratio of solvent-to-oil, the thermodynamic driving force resulting from the selection of the solvent system and the temperature of contact.
  • the raffinate so produced will contain a minimum amount of solvent, generally less than 10% and typically 2-5%, and the extract will contain the remainder of the solvent feed.
  • the COS will be higher than 50%> and will typically and most desirably exceed 65%.
  • Raw kerogen oil possessing 1.6%N and an average molecular weight of 325 Dalton was fed to the bottom of a countercurrent liquid-liquid contacting column refilled with selected solvent system while fresh extraction solvent comprised of 90% formic acid and 10% water was fed to the top of the column.
  • the ratio of feed to fresh solvent was 1 :1.
  • an extract comprised substantially of heteroatom-containing compounds and a majority of solvent was withdrawn from the bottom of the column.
  • a raffinate comprised substantially of non-heteroatom- containing hydrocarbons and a minority of solvent was withdrawn from the top of the column.
  • the measured polar oils (extract) comprised 30%) of the feed material and exhibited 4.3% nitrogen.
  • the recovered non-polar oils comprised approximately 70% of the feed material and exhibited 0.45%N.
  • the recovery of nitrogen compounds is 80.4%.
  • the coefficient-of-separation is 80.3%) indicating essentially no non-nitrogen compounds in the extract.
  • the raffinate and the extract are separately charged to a distillation apparatus as shown in Figure 4 where they are heated to vaporize the formic acid/water solvent for recovery and recycle to the extraction system.
  • solvent recovery by distillation will be aided by the presence of cycloparaffins and aromatics which form azeotropes with the selected formic acid/water system.
  • the condensate of this vapor will form two phases, a lower phase comprised principally of formic acid and water which is drawn off for recycle to the extraction system and an upper phase comprised principally of low boiling naphthenic and aromatic hydrocarbons which are drawn off and returned to the respective concentrate from which they came.
  • a portion of the naphthenic and aromatic light hydrocarbon material separated from the distillation condensate may be recycled to the concentrate prior to distillation to enhance the recovery of selected solvent through stripping and enhanced azeotropic effect.
  • Light hydrocarbon material recovered from the raffinate stripping column may be added to the bottoms of the solvent recovery column to aid with stripping of solvent from the extract (details not shown in Figure 4).
  • a fraction of this naphthenic/aromatic light hydrocarbon material may be recycled to the kerogen oil prior to presaturation with selected solvent to modify the solvent properties of the oil phase for purposes of enhancing the COS while minimizing the solvent-to-oil ratio.
  • Table VI The mass balance for a typical process of solvent recovery, modeled from thermodynamic properties is given in Table VI.
  • the raffinate which has been stripped of selected solvent may be used directly as a petroleum refinery feed or it may be further processed to enhance its value.
  • the extract from which the solvent has been removed may be used directly or it may be further processed to enhance its value.
  • Direct Use of Extract Preferably, direct use of extract will be made in markets for which there is a high- volume. High- volume applications minimize important limitations on the capacity of the plant. Examples of high volume uses to which the raw extract may be made are additives for improving the properties of asphalt, surfactants for improving interfacial properties of mixed phases, solvents for dissolution or dispersion of solids and precipitates, fuels, and materials constructed through the polymerization or derivitation of the extract.
  • the terms "direct use” and "high- volume” are generally interchangeable .
  • a high nitrogen antistrip additive produced by extraction of polar heteroatom- containing compounds from raw kerogen oil was tested for its antistripping characteristics by a Water Susceptibility Test (WST).
  • WST Water Susceptibility Test
  • the antistrip additive was mixed with an asphalt binder.
  • Rheological measurements were made on the stripping-prone, neat asphalt and the asphalt-additive mixture to ensure that the additive did not adversely affect the asphalt viscosity. Viscosity measurements at 25°C and 60°C showed the viscosity reduction to be within acceptable limits.
  • Briquettes consisting of five mass percent asphalt and asphalt with 4% extract with 20-35 mesh aggregate particles were made following the Plancher et al. procedure as described in "Canadian Technical Asphalt Association Proceedings", vol. XXV, p. 246-262, Nov.
  • Cycles to failure greater than 12 are considered to be essentially equivalent and very moisture insensitive.
  • Alkyl-substituted pyridines extracted from kerogen oil can be converted to cationic surfactants by reaction with alkyl chlorides.
  • the resulting quaternary pyridinium surfactants ("quats") will be quite different from commercial materials due to the long-chain alkyls attached to the pyridinic ring. This will result in unique behavior and properties.
  • cationic surfactants are quaternary aliphatic ammonium compounds, but the marketplace includes quite a variety of variations on these themes.
  • An example of the pyridine derivatives is cetylpyridinium chloride, used in a number of personal care products.
  • Quaternary ammonium surfactants are used in a broad variety of consumer and industrial formulations (Table VII).
  • a major traditional application is in disinfectants, taking advantage of the bactericidal properties of many of these compounds.
  • the largest businesses are in consumer products, because of the importance of fabric softeners, virtually all of which are quats made from aliphatic amines.
  • the other rapidly growing application is in hair conditioners, the largest application in personal care products.
  • Table VII Cationic Surfactants
  • pyridine-derived quats have the nitrogen buried in the middle, with a long alkyl chain on the nitrogen. Surfactant properties are controlled by altering the lengths of the chain to give varied solubility, interfacial activity, etc.
  • the quats made from kerogen oil would be similar, except that the long chain would be on the ring.
  • the opportunity comes from using a methyl or ethyl group on the nitrogen and relying on the long alkyl chain attached to the ring as the fatty end.
  • the cationic site thus has the acid/base properties one would expect from a nitrogen in a pyridine yet the oleophilic/hydrophilic properties are those of a long-chain alkyl making a "fatty pyridine".
  • kerogen-derived pyridines could be used as surfactants without N-alkylation.
  • small amounts of mineral acid could be added to form the pyridinium cation.
  • naturally occurring acidic species would convert the pyridine to a pyridinium. The cost for production of such quats is also low because methyl or ethyl substitution is inexpensive on a molar basis.
  • the uniqueness of kerogen-derived pyridines is both an advantage and a disadvantage.
  • the advantage comes from the lack of competitive materials. Making a "fatty pyridine" from conventional synthetic pyridine requires something akin to Friedel-Crafts alkylation of benzene, except that the reaction will probably require an extra step to protect the N from substitution by the alkyl chloride.
  • the disadvantage comes from the absence of identified market for these materials. For these reasons it was not possible to test for market acceptability of these potential products.
  • pyridinic kerogen oil extract may be used to remove sludge from tank bottoms, pipelines and other industrial equipment. These extracts may be useful for metal winning oils in metallurigical applications or for anticorrosion additives. Phenolic concentrates may be used for solution of sludges or for pour point depressants in petroleum application.
  • a preferred step in the processing of extract is to distill the extract into a distillate fraction and a bottoms or residue fraction.
  • the distillate fraction and bottoms fractions are subsequently separately processed.
  • the distillate fraction may be used directly as a light industrial solvent or it may be sent to hydrodealkylation processing to remove alkyl groups leaving the parent ring systems substantially free of alkyl and methyl groups.
  • the residue fraction may be used directly for uses similar to the total extract or it may be subjected to cracking to reduce its average molecular weight.
  • the extract may be distilled into a light and heavy distillate and a bottoms.
  • the light distillate may be used directly or sent to thermal hydrodealkylation processing
  • the heavy distillate may be sent to a cracking process to reduce its molecular weight
  • the bottoms may be used directly or processed to manufacture asphalt additives, ionic surfactants, dispersants or the like.
  • the extract contains heterocyclic compounds that have methyl groups and longer alkyl chains attached to the ring(s). These methyl and alkyl groups must be cracked from the ring(s) to reduce the molecule to its parent ring(s) system. In general, such cracking may occur either catalytically or thermally. Catalytic cracking over solid Si-Al catalysts may be used for feedstocks of low nitrogen content such as for Kukersite kerogen oil extract.
  • a Kukersite shale oil extract comprising in excess of 35 weight percent of the total kerogen oil and containing in excess of 80% hydroxyaromatics may be catalytically cracked to yield a crackate product comprised predominantly of mono- an di-hydroxyaromatics.
  • These hydroxyaromatics may contain methyl and ethyl substituents that may be removed by THDA as described further below.
  • Catalytic cracking may be performed by any convenient commercial process used today in the petroleum industry.
  • a high nitrogen extract which tends to react unfavorably with solid Si-Al catalyst, may be thermally cracked either by coking or by hydropyrolysis. Coking may be performed by any convenient commercial process used today in the petroleum industry.
  • Hydropyrolysis is a short contact time, thermal hydrocracking process. (See Flow Diagram in Figure 5.)
  • the objective of hydropyrolysis is to crack alkyl chains without producing coke from pyridines, phenols or aromatics.
  • hydropyrolysis it is desirable to inhibit dehydrogenation of naphthenes.
  • the high hydrogen pressure and short contact times accomplish this. If the feedstock contains material that cannot be vaporized at the reaction temperature and pressure the reactor system must accommodate a mixed phase. It is undesirable to 'over-crack' because to do so generates non-condensable gases which are of less value than liquids and which result in high hydrogen consumption.
  • hydropyrolysis of a >290 °C extract from a Green River Formation kerogen oil at 540 °C, 1500 psi H 2 pressure, and 6-30 sec residence time yielded 82 to 85% liquids, 7 to 12% gases and 5 to 9% coke.
  • the amount of coke can be reduced to nearly zero because coke is formed only when droplets impinge on the reactor walls.
  • a small amount of water is also observed, which results from hydropyrolysis of oxygen-containing compounds. Methane is the predominant gaseous component.
  • the analysis of the hydropyrolysis liquid products shows small amounts of pyridine and picolines and large amounts of tri- and tetra-methylated pyridines. Because most of the pyridines in the kerogen oil are tri- and tetra- substituted and hydropyrolysis is not designed to demethylate, the low concentrations of picoline and pyridine are expected. The observed results are consistent with the compositional analysis and expected chemistry. The demethylation of methyl substituted pyridines may be accomplished through additional crackate processing as described further below.
  • the crackate obtained from cracking of extract contains numerous components comprised of the ring systems with methyl groups and short alkyl chains attached and hydrocarbon products that were the long alkyl groups attached to the rings in the original extract. This process stream must be further processed before it is of appreciable use.
  • a preferred approach is to recycle the cracked products or crackate to the extraction step where the heteroatom-containing ring systems are extracted along with heteroatom-containing compounds originally in the hydrocarbonaceous oil. With the recycle of the crackate, the efficiency of the extraction step also improves. The lower viscosity and the 'solvating' effect of lighter polar compounds helps extract the heavier polar compounds that have long alkyl chains attached and have an appreciable affinity for the raffinate fraction.
  • liquid product (crackate) obtained from hydropyrolysis obtained from hydropyrolysis
  • the nitrogen content of the polar extract was measured at 6.0%).
  • GC/MSD analysis of the polar extract of the HP products showed that the majority of the identifiable compounds are pyridine derivatives. Alkyl pyrroles, quinolines, isoquinolines, indoles, and carbazoles are also identified.
  • the polar extract may be topped by distillation.
  • topping temperature is made to control the composition of the light distillate. For example, if naphthalene, quinoline or other higher ring aromatics are not desired products then the topping might be conducted at 200°C or less. If these dicyclic types are desired, the topping temperature may be raised to include these types.
  • Such reasoning may also be applied to distillation of high oxygen content hydrocarbonaceous oils where it may be desirable to separate dihydroxybenzenes (such as resorcinols, from monohydroxybenzenes such as phenols). In practice, fractionation of the extract may be made flexible enough to change product objectives as market conditions dictate.
  • the temperature of the heavy distillate cutpoint can be selected so as to enhance the operation of the cracking unit.
  • the cutpoint is selected at about 350°C the distillate that is lighter than 350°C material may be sent to the cracking unit in the vapor phase reducing operating difficulties. In such a case the coke formation will be minimal.
  • the cutpoint for the distillation may be increased to about 530°C atmospheric equivalent boiling point (the actual distillation is conducted under high vacuum to avoid cracking in the distillation step) and the lighter than 530°C material is sent to the cracking unit. This alternative is contemplated when catalytic cracking is employed or when higher yields of low molecular weight heteroatom-containing compounds are desired.
  • a key feature of the preferred scheme is the use of HP, coking or catalytic cracking to crack alkylated types to their methylated homologs thereby concentrating these types in a narrow and predictable boiling range.
  • the extract may be distilled as described.
  • the ⁇ 200°C extract may now be subjected to vapor-phase thermal hydrodealkylation THDA, to demethylate the rings.
  • Process conditions for this step are similar to those used when hydrodealkylating toluene to benzene, namely, T >600°C, P H2 1000 psi, t ⁇ 60 seconds. Steam may also be added to reduce coke formation and enhance the process operability.
  • the flow diagram for this step is shown in Figure 2.
  • the feedstock is derived from Green River Formation kerogen oil then the primary products from THDA are pyridines, pyrroles and single ring aromatics. Products that possess boiling points higher than the desired end products may be recycled for further dealkylation. If extract is from a Kukersite kerogen oil the distillation may be performed at a temperature of about 300 °C and the THDA be operated to produce phenol, cresols, resorcinol and methyl resorcinols.
  • a separation scheme for product refinement is given in Figure 3.
  • the scheme is designed to maximize the purity of pyridine and ° -picoline (2-methylpyridine).
  • the major separation problem in purifying pyridine is the presence of toluene and methylthiophenes that possess similar boiling points.
  • the major separation problem in purifying alpha-picoline is the presence of pyrrole and, to a lesser extent, C8 aromatics. Streams other than pyridine and alpha-picoline are comprised of aromatic byproducts that also have an appreciable market value.
  • a similar process sequence is contemplated for high oxygen kerogen oils such as those produced from Kukersite oil shale or Eastern Queensland Tertiary oil shale (Australia).
  • the extract may first be divided into light, middle and heavy fractions with the middle fraction hydropyrolyzed or catalytically cracked for primary dealkylation and the dealkylated material is then re-extracted to produce a concentrate of oxygen rich components, primarily phenolics. This concentrate may then be directly separated for pure compounds or further processed in THDA to further dealkylate methyl groups prior to purification.
  • the product of a raffinate that is low in heteroatom-containing molecules and high in non-heteroatom-containing compounds and resulting from an extraction of hydrocarbonaceous oil exhibiting a coefficient-of-separation greater than 50% may be used for the following applications:
  • a primary use contemplated for the raffinate is as a substitute petroleum feedstock. Removal of heteroatoms renders the raffinate more easily processed to petroleum products.
  • the raffinate may be sent directly to a petroleum refinery without further upgrading and processed to manufacture a traditional product slate of motor gasoline, diesel fuel, jet fuel, waxes, lube oils and the like.
  • the raffinate may be catalytically hydroprocessed to further remove nitrogen, sulfur or oxygen heteroatoms and to hydrogenate unstable olefins. If this step is performed the resulting product is a premium- value, sweet synthetic crude oil.
  • the compound type distribution of the feedstock and the products is given in Table X and shows a reduction in olefins and aromatics due to hydrogenation and an increase in isoparaffins due to ring opening.
  • the raffinate may be distilled to separate the raffinate into distillate and a residue.
  • the cutpoint for such a distillation may be similar to the cutpoint made in a petroleum refinery in the atmospheric (crude) tower.
  • the distillate may be sent to a catalytic hydrotreater as described above while the residue boiling in the gas oil range may be sent to a catalytic cracker.
  • the residue from the distillation step is an acceptable feedstock to a catalytic cracking unit because it is low in basic nitrogen as a result of the extraction of polar nitrogen compounds as a practice of the invention.
  • the gas oil range material is cracked over an acid (Si-Al) catalyst where high-octane gasoline components are produced directly.
  • the catalytically hydroprocessed sweet refinery feed may be distilled and the distillate sent to process for manufacture of motor gasoline, diesel fuel, kerosene, jet fuel and the like, while the residue from the distillation may be sent to a catalytic cracker for manufacture of high octane gasoline components.
  • a catalytic cracker for manufacture of high octane gasoline components.
  • Other uses of the raffinate may be made as a consequence of the low heteroatom content achieved through the practice of the invention.
  • light naphtha may be fed to steam cracking for manufacture of olefins and aromatics.
  • Benzene, toluene and xylenes (BTX) may be extracted from the naphtha.
  • BTX toluene and xylenes
  • a hydrocarbonaceous oil is extracted by a selected solvent system chosen so as to maximize the coefficient-of-separation of the desired heteroatom-containing compounds while minimizing the solvent-to-oil ratio and yielding acceptable recovery of solvent and the extraction yielding a coefficient-of-separation of at least 50% and typically greater than 65% of desired heteroatom-containing compounds in the extract fraction.
  • the extract is distilled into three fractions, the bottoms being used directly for commercial use, the heavy distillate being sent to a cracking unit where substantially all of the alkyl side chains are removed from the heteroatom-containing rings leaving the methylated homologs, the crackate being recycled to the extraction unit where heteroatom-containing compounds are recovered in the extract and non- heteroatom-containing compounds, that were the alkyl side groups in the original extract, are recovered in the raffinate.
  • the light distillate that contains low molecular weight heteroatom-containing compounds originally in the hydrocarbonaceous oil along with additional low molecular weight heteroatom-containing compounds that were produced in the cracking process are sent to a thermal hydrodealkylation unit where substantially all of the methyl groups are removed from the heteroatom-containing rings and the products of THDA purified for their pure compound values by distillation, extraction, crystallization, adsorption, derivitization, or other appropriate means.
  • the raffinate of the extraction which contains the non-heteroatom-containing compounds in the original hydrocarbonaceous oil plus any non-heteroatom-containing compounds produced in the cracking unit and subsequently separated in the extraction step is sent to a catalytic hydroprocessing unit to produce a sweet synthetic crude oil.
  • FIG. 6 An overall alternative preferred process of the invention is shown in Figure 6.
  • a hydrocarbonaceous oil is extracted by a selected solvent system chosen so as to maximize the coefficient-of-separation of the desired heteroatom-containing compounds while minimizing the solvent-to-oil ratio and yielding acceptable recovery of solvent and the extraction yielding a coefficient-of-separation of at least 50% and typically greater than 65% of desired heteroatom-containing compounds in the extract fraction.
  • the extract is distilled into two fractions, the bottoms being sent to a cracking unit where substantially all of the alkyl side chains are removed from the desired heteroatom-containing rings, the crackate being recycled to the extraction unit where heteroatom-containing compounds are recovered in the extract and non- heteroatom-containing compounds, that were the alkyl side groups in the original extract, are recovered in the raffinate.
  • a drag stream of non-volatiles from the cracking unit may be withdrawn, if desired, to prevent buildup of the heaviest materials.
  • the light distillate that contains low molecular weight heteroatom-containing compounds originally in the hydrocarbonaceous oil along with additional low molecular weight heteroatom-containing compounds that were produced in the cracking process are sent to a thermal hydrodealkylation unit where substantially all of the methyl groups are removed from the heteroatom-containing rings and the products of THDA purified for their pure compound values by distillation, extraction, crystallization, adsorption, derivitization, or other appropriate means.
  • the raffinate of the extraction which contains the non-heteroatom-containing compounds in the original hydrocarbonaceous oil plus any non-heteroatom-containing compounds produced in the cracking unit and subsequently separated in the extraction step is sent to a catalytic hydroprocessing unit to produce a sweet synthetic crude oil.
  • a second alternative preferred process of the invention is shown in Figure 7.
  • a hydrocarbonaceous oil is extracted by a selected solvent system chosen so as to maximize the coefficient-of-separation of the desired heteroatom-containing compounds while minimizing the solvent-to-oil ratio and yielding acceptable recovery of solvent and the extraction yielding a coefficient-of-separation of at least 50% and typically greater than 65%o of desired heteroatom-containing compounds in the extract fraction.
  • the extract is used directly for commercial use, or directly or as a feedstock for manufacture of commercial products.
  • the raffinate of the extraction which contains the non-heteroatom-containing compounds in the original hydrocarbonaceous oil, is sent to a catalytic hydroprocessing unit to produce a sweet synthetic crude oil.

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Abstract

L'invention concerne un procédé de raffinage des huiles d'hydrocarbures contenant des composés renfermant des hétéroatomes. Les huiles d'hydrocarbures entrent en contact avec un système solvant, à savoir un mélange composé, en grande partie, d'un solvant polaire ayant un moment dipolaire supérieur à environ 1 debye et, en moindre quantité, d'eau afin de séparer par sélection les éléments constitutifs des huiles carbonées en une fraction de raffinat sans hétéroatomes et une fraction d'extrait enrichie en hétéroatomes. Le solvant polaire et le système solvant aqueux sont préparés selon une proportion d'antisolvant, sous forme d'eau, en quantité suffisante pour inhiber la solubilité des composés renfermant des hétéroatomes et du solvant polaire dans le raffinat et de manière à inhiber la solubilité de composés contenant des non hétéroatomes dans l'extrait. Le rapport des huiles d'hydrocarbures avec le système solvant est tel que le coefficient de séparation est d'au moins 50 % et qu'il représente le pourcentage de molécule/gramme de composés renfermant des non hétéroatomes extraits des huiles carbonées récupérées dans la fraction d'extrait. L'extrait exempt de solvant et les concentrés de raffinat peuvent être utilisés directement ou traités pour obtenir des produits pétroliers, chimiques ou industriels d'intérêt.
PCT/US2000/014128 1999-05-24 2000-05-23 Procede d'amelioration de la valeur des ressources naturelles d'hydrocarbures Ceased WO2000071494A1 (fr)

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WO2011071733A1 (fr) * 2009-12-08 2011-06-16 Exxonmobile Research And Engineering Company Elimination de composés azotés d'un distillat issu du craquage catalytique fcc
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US9643902B2 (en) 2010-12-07 2017-05-09 Exxonmobil Chemical Patents Inc. Processes utilizing solvent extraction
WO2012078218A1 (fr) 2010-12-07 2012-06-14 Exxonmobil Chemical Patents Inc. Procédé utilisant une extraction par solvant
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WO2014182499A1 (fr) * 2013-05-07 2014-11-13 Kior, Inc. Procédé de valorisation de produits dérivés d'une biomasse, par utilisation d'une extraction liquide-liquide
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