WO2019094378A1 - Extraction d'hydrocarbures à partir de matière particulaire - Google Patents

Extraction d'hydrocarbures à partir de matière particulaire Download PDF

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Publication number
WO2019094378A1
WO2019094378A1 PCT/US2018/059430 US2018059430W WO2019094378A1 WO 2019094378 A1 WO2019094378 A1 WO 2019094378A1 US 2018059430 W US2018059430 W US 2018059430W WO 2019094378 A1 WO2019094378 A1 WO 2019094378A1
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Prior art keywords
composition
hydrocarbon
water soluble
ammonium
salt
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PCT/US2018/059430
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English (en)
Inventor
Aron Lupinsky
Bruce G. Miller
Paul C. PAINTER
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Extrakt Process Solutions, Llc
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Priority to CA3082029A priority Critical patent/CA3082029A1/fr
Publication of WO2019094378A1 publication Critical patent/WO2019094378A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/045—Separation of insoluble materials
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/047—Hot water or cold water extraction processes
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW

Definitions

  • the present disclosure relates to separating and recovering hydrocarbons, e.g., bitumen and oil, from compositions including such hydrocarbons and solids.
  • hydrocarbon compositions include, for example, oil sands, bitumen froth, pitch materials, hydrocarbon contaminated rock, soil, etc.
  • a number of treatment options can be applied to oil contaminated sand and rocks, including incineration, distillation, washing with detergents, extraction using organic solvents or bioremediation. Some of these methods have proved to be uneconomic because of their energy requirements, others do not completely remove the oil from the sand, or the chemicals used may pose unacceptable environmental concerns. None of these methods appear to be entirely satisfactory, but long-term storage (e.g., in landfills) of oil-contaminated sand is also a major problem.
  • the preferred solution would be to recover the oil for its economic value while generating sand in a clean form so that it can be used to repair environmental scars. This is not easy, because at least for waste materials the oil has usually weathered, lost much of its volatile component and is in the form of a viscous sludge or tar balls.
  • An advantage of the present disclosure is a process to separate hydrocarbons from compositions including such hydrocarbons intermixed with solids in high yields. Such separated hydrocarbons can advantageously contain a low amount of fines or mineral content. The process of the present disclosure further advantageously can have an improved impact on the environment.
  • a process for separating hydrocarbon from a composition comprising hydrocarbon and solids.
  • the process comprises treating the composition with an aqueous mixture including at least one highly water soluble salt, and optionally at least one polymer flocculant and optionally at least one organic diluent to separate the hydrocarbon from the composition.
  • an extraction mixture can separate the hydrocarbon from the composition in high yields, e.g., at least about 80%, such as at least about 85% or about 90% or higher, of the hydrocarbon included in the composition.
  • the hydrocarbon directly separated from treating the composition can advantageously contain a low amount of fines and/or minerals, e.g., less than about 1 wt% or no more than about 0.5 wt% or no more than about 0.1 wt%.
  • aspects of the present disclosure include, for example, treating a hydrocarbon composition with an aqueous mixture including at least one highly water soluble salt: (i) wherein the treated composition has a salt-composition concentration of the at least one highly water soluble salt of at least 0.5 wt%, (ii) wherein treating the composition does not include increasing a temperature of the composition by more than about 10 °C, e.g., no more than about 5 °C, to separate the hydrocarbon from the composition, (iii) wherein treating the composition does not include injecting a gas, such as air or nitrogen, in to the composition to create a froth, (iv) wherein treating the composition does not include use of a significant amount, e.g., no more than 0.05 wt%, of alkali metal hydroxide salt(s) to separate the hydrocarbon from the composition; or any combination thereof.
  • a gas such as air or nitrogen
  • aqueous mixture can advantageously include a significant amount of the one or more highly water soluble salt(s) and at least a portion thereof can be recycled to treat additional hydrocarbon compositions.
  • the recovered hydrocarbon can include diluent when used to treat the composition and at least a portion of such diluent can be recovered and recycled to treat additional hydrocarbon compositions.
  • the hydrocarbon composition comprises Canadian oil sands including bitumen, bitumen froth from a Canadian oil sands process and/or hydrocarbon containing a by-product of Canadian oil sands processes.
  • the composition can include a significant amount by weight of fines.
  • the hydrocarbon directly separated from treating the composition can advantageously contain a low amount of fines and/or minerals, e.g., less than about 1 wt% or no more than about 0.5 wt% or no more than about 0.1 wt%.
  • the at least one highly water soluble salt is an ammonium based salt such as an ammonium chloride, ammonium sulfate or combinations thereof.
  • the treated composition can have a salt-composition concentration of the highly water soluble salt(s) of at least 0.5 wt% and/or a polymer-composition concentration of the polymer flocculant(s) of no less than zero and up to about 0.001 wt%, e.g., up to about 0.005 wt%.
  • treating the composition includes using a solution of one or more highly soluble salts sourced from a natural or existing source, e.g., seawater or a body of hypersaline water.
  • the processes of the present disclosure can be practiced at relatively low temperatures and without addition of a significant amount of, or any of, an alkali metal hydroxide salt or carboxylate salt.
  • Figure 1 is a picture of a vial showing bitumen separated from Kentucky oil sands by a separating mixture according to an embodiment of the present disclosure.
  • Figure 2 is a comparison of the infrared spectra of an original Kentucky oil sands sample to the extracted residual mineral matter.
  • Figure 3 shows infrared spectra of two films of bitumen separated from
  • Kentucky oil sands by a separating mixture according to an embodiment of the present disclosure.
  • Figure 4 is a picture of vials containing Kentucky oil sands that were treated in various ways.
  • Figure 5 is a picture of vials containing Canadian oil sands that were treated in various ways.
  • Figure 6 shows infrared spectra comparing bitumen separated from Canadian oil sands to the extracted residual sand.
  • Figure 7 shows infrared spectra comparing an original Canadian oil sands sample to the extracted residual sand.
  • Figure 8 shows pictures of vials containing samples of (left) extracted mineral matter and (right) recovered bitumen from Kentucky oil sands.
  • Figure 9 shows infrared spectra comparing bitumen separated from Kentucky oil sands to the extracted residual mineral matter.
  • Figure 10 shows a picture of a vial containing Canadian oil sands that were treated with seawater.
  • the present disclosure relates to separating hydrocarbon from compositions including the hydrocarbon intermixed with or attached to inorganic solids.
  • hydrocarbon compositions also include water, either in their native form or added during processing of the hydrocarbon compositions.
  • the inorganic solids include, for example, rock, sand, mineral matter, e.g., minerals and mineral like materials such as clays, and silt, hereinafter referred to as solids.
  • Hydrocarbon compositions that can be separated according to the processes of the present disclosure include oil sands, bitumen froth, or hydrocarbon containing by products of oil sands production, asphalt compositions and pitch materials and other natural and non-natural asphalt containing compositions, hydrocarbon contaminated solids such as hydrocarbon contaminated sand, such as in Kuwait, hydrocarbon contaminated rock, soil, hydrocarbon waste products containing solids such as oily sludge etc.
  • the hydrocarbons can include tar, crude oil, heavy oil, or other hydrocarbon oil, bitumen, asphaltenes, etc.
  • the process includes treating, by mixing, combining, contacting, etc., a composition comprising hydrocarbon and solids with an aqueous mixture including at least one highly water soluble salt to separate the hydrocarbon from the composition.
  • the mixture can optionally also include at least one water soluble polymer, e.g., a polymer flocculant, and/or optionally include at least one organic diluent to separate the hydrocarbon from the composition.
  • Such a treated composition can form multiple phases including a hydrocarbon phase, an aqueous phase and an aggregated solids phase.
  • the hydrocarbon phase would include organic diluent, while the aqueous phase would include aqueous components.
  • a separating fluid including water and the salt(s), polymer(s) and organic diluent(s) can separate hydrocarbon from hydrocarbon compositions in high yields e.g., at least about 80%, such as at least about 85% or about 90% or higher, of the hydrocarbon included in the composition. All percentages used herein are by weight unless specified otherwise. It is believed that the highly water soluble salt(s) in the separating fluid facilitate extraction in a number of ways, including: reducing the attraction between hydrocarbons and mineral surfaces. The highly water soluble salt(s) aid in aggregating solids in the compositions, particularly fine solids which can be difficult to aggregate.
  • the polymer acts in concert with the salt(s) to sequester solids, particularly fines, and to minimize emulsion formation in the treated composition.
  • the organic diluent(s) aid in separating the hydrocarbon and lowers the viscosity of viscous hydrocarbons separated from the composition, which aids in recovering the hydrocarbons.
  • coagulation and flocculation are often used interchangeably in the literature.
  • coagulation means particle aggregation brought about by the addition of salts
  • flocculation means particle aggregation induced by flocculating polymers.
  • Aggregation induced by the addition of salts is believed to be the result of destabilizing the particles suspended in the fluid by an alteration or a shielding of the surface electrical charge of the particles to reduce the inter-particle repulsive forces that prevent aggregation
  • aggregation induced by flocculation is believed to be the result of the polymer binding to the particles thereby tying the particles together into a so called floe causing aggregation of the particles.
  • Hydrocarbon separated from the treated composition can then be recovered from the treated composition by any number of processes useful for recovering hydrocarbon separated from solids and an aqueous mixture such as by skimming, decanting, distilling, centrifuging, etc. using such devices such as decanters, distillation columns, pressure separators, centrifuges, open tank, hydrocy clones, settling chambers or other separators, etc.
  • the hydrocarbon directly separated from the composition can contain a low amount of fines.
  • fines as used herein is consistent with the Canadian oil sands classification system and means solid particles with sizes equal to or less than 44 microns ( ⁇ ). Sand is considered solid particles with sizes greater than 44 ⁇ .
  • Many of the hydrocarbon compositions that can be treated according to the present disclosure include a significant amount by weight (>5%) of fine solids.
  • oil sands deposits include approximately 10-30 wt% of solids as fines.
  • Such fines are typically in the form of minerals or mineral like materials and recovered hydrocarbon with a high minerals content can be problematic in processes involving subsequent refining or upgrading of recovered hydrocarbon since the minerals interfere with such processes.
  • compositions which have a significant amount by weight of solids as fines (>5%) are treated.
  • Such compositions can be treated with an aqueous mixture including at least one highly water soluble salt, at least one polymer flocculant, and at least one organic diluent to separate the hydrocarbon from the composition.
  • the hydrocarbon directly separated from the composition by treating the composition with the aqueous mixture can contain a low amount of fines or has low minerals content, e.g., less than about 1 wt% or no more than about 0.5 wt% or no more than about 0.1 wt%.
  • no intervening step is needed between separating the hydrocarbon from the treated composition and recovering the hydrocarbon to produce hydrocarbon with a low amount of fines.
  • the determination of fines content can be assessed by detecting for mineral matter content in the separated hydrocarbon by infrared spectroscopy, x-ray diffraction, ash content or by an equivalent method.
  • Salts that are useful in practicing processes of the present disclosure include salts that are highly soluble in water.
  • a highly water soluble salt as used herein is one that has a solubility in water of greater than 2 g of salt per 100 g of water (i.e., a salt/water solubility of 2g/100g) at 20 °C.
  • the highly water soluble salt has a water solubility of at least about 5 g/100 g at 20 °C, e.g., at least about 10 g/100 g of salt/water at 20 °C.
  • the highly water soluble salts used in the processes of the present disclosure are preferably non-hydrolyzing.
  • Hydrolyzing salts undergo hydrolysis when added to water to form metal hydroxides, which precipitate from solution.
  • Such hydrolyzing salts are believed to form open floes with inferior solids content and cannot be readily recycled for use with additional hydrocarbon compositions in continuous or semi-continuous processes.
  • hydrolyzing salts typically have low solubility in water and are used at elevated temperatures to ensure sufficient solubility for aggregation, which is an energy intensive process.
  • the highly water soluble salts are preferably not ionic liquids (i.e., salts having a melting point below 100 °C). Ionic liquids can be expensive and may need to be reduced to low levels on the extracted solids, e.g., sand.
  • the highly water soluble salts are preferably not carboxylate salts since such organic acid salts tend to be more expensive than inorganic salts and can be deleterious to plant and/or animal life.
  • the highly water soluble salts are preferably not alkali metal hydroxide salt(s), such as lithium, sodium or potassium hydroxide, since such alkali metal hydroxide salt(s) tend to require elevated temperatures to be effective and can significantly increase the alkalinity of the treated composition.
  • Highly water soluble salts that are not hydrolyzing and useful in practicing processes of the present disclosure include salts having a monovalent cation, e.g., alkali halide salts such as sodium chloride, potassium chloride; also salts with monovalent cations such as sodium nitrate, potassium nitrate, sodium and potassium phosphates, sodium and potassium sulfates, etc. are useful in practicing processes of the present disclosure.
  • ammonium based salts such as ammonium acetate (NH4C2H3O2), ammonium chloride (NH 4 CI), ammonium bromide (Nf ⁇ Br), ammonium carbonate ((NH 4 ) 2 C0 3 ), ammonium bicarbonate (NH 4 HCO 3 ), ammonium nitrate (NH 4 NO 3 ), ammonium sulfate ((NH ⁇ SC ), ammonium hydrogen sulfate (NH 4 HSO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), ammonium hydrogen phosphate ((NH ⁇ HPC ), ammonium phosphate ((NH ⁇ PC ), etc. Mixtures of such salts can also be used.
  • ammonium based salts such as ammonium acetate (NH4C2H3O2), ammonium chloride (NH 4 CI), ammonium bromide (Nf ⁇ Br), ammonium carbonate ((NH 4 ) 2 C0 3 ), am
  • Ammonium based salts are useful for practicing the present disclosure since residual ammonium based salts that remain on the solids are not harmful to plant life and thus can more readily allow disposal of the solids such as in landfills.
  • many of the ammonium based salts are useful as fertilizers and are in fact beneficial to plant life, e.g., ammonium chloride, ammonium nitrate, ammonium sulfate, etc.
  • Many of the monovalent sulfate and phosphate salts are also useful as fertilizers.
  • the highly water soluble salt or salts used in the processes of the present disclosure can preferably be non-toxic and beneficial to plant life to aid in environmental remediation and the restoration of mine sites.
  • Such highly water soluble salts include ammonium based salts and/or phosphate based salts.
  • Highly water soluble salts that can be used in practicing the present process can also include salts having multivalent cations.
  • Such salts include, for example, divalent cation salts such as calcium and magnesium cation salts, such as calcium chloride (CaCl 2 ), calcium bromide (CaBr 2 ), calcium nitrate (Ca(N0 3 ) 2 ), magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), magnesium nitrate (Mg(N0 3 ) 2 ), magnesium sulfate (MgSC ⁇ ); and trivalent cation salts such as aluminum and iron (III) cation salts, e.g., aluminum chloride (AICI 3 ), aluminum nitrate (A1(N0 3 ) 3 ), aluminum sulfate (A1 2 (S0 4 ) 3 ), iron (III) chloride (FeCl 3 ), iron (III) nitrate (Fe(N0 3 )
  • multivalent salts can increase fouling of containers and formation of less cohesive consolidated materials as compared to highly water soluble salts having monovalent cations.
  • some multivalent salts such as FeCl 3 and Fe 2 (S0 4 ) 3 , are particularly corrosive and Fe 2 (S0 4 ) 3 is formed from oxidizing pyrite and results in acid mine run-off, which make such salts less preferable for use in processes of the present disclosure.
  • the concentration of the at least one highly water soluble salt should preferably be at least 0.5 wt% and preferably no less than about 1 wt%, such as at least about 2 wt% and even at least about 3 wt%, 4 wt%, 5 wt%, 7 wt%, 8 wt%, 10 wt%, or higher in the aqueous mixture.
  • the concentration of the highly water soluble salt in the aqueous separating mixture can be increased to account for the significant water in the composition.
  • a natural source of a highly soluble salt or salts such as in a natural body of water including such salts in sufficiently high concentration such as at least about 2 wt% and even at least about 3 wt% or greater.
  • ocean or seawater can be used as a source of highly soluble salts, which can significantly improve the economics of the process under certain conditions.
  • the vast majority of seawater has a salinity of between 31 g/kg and 38 g/kg, that is, 3.1-3.8%.
  • seawater in the world's oceans has a salinity of about 3.5% (35 g/L, 599 mM).
  • Seawater includes of a mixture of salts, containing not only sodium cations and chlorine anions (together totaling about 85% of the dissolved salts present), but also sulfate anions and calcium, potassium and magnesium cations. There are other ions present (such as bicarbonate), but these are the main components.
  • Another natural source of highly soluble salts that can be used as a source of highly soluble salts includes a hypersaline body of water, e.g., a hypersaline lake, pond, or reservoir.
  • a hypersaline body of water is a body of water that has a high concentration of sodium chloride and other highly soluble salts with saline levels surpassing ocean water, e.g., greater than 3.8 wt% and typically greater than about 10 wt%.
  • Such hypersaline bodies of water are located on the surface of the earth and also subsurface, which can be brought to the surface as a result of oil sands mining operations.
  • the aqueous mixture used in separating hydrocarbon from compositions can include a water soluble polymer flocculant.
  • a water soluble polymer flocculant in the processes of the present disclosure can advantageously aid in aggregating solids in the treated composition and can also minimize formation of emulsions in the treated composition.
  • Emulsions also referred to as a rag layers, can form at the interface of a hydrocarbon and aqueous phase in treated compositions. It is believed that rag lays are stabilized by fine solids and certain hydrocarbons such as asphaltenes in hydrocarbon compositions. Such emulsions can be difficult to demulsify when formed and typically result in a large amount of fines in the hydrocarbon phase.
  • Polymers that are useful in practicing the present disclosure include water soluble flocculating polymers such as polyacrylamides or copolymers thereof such as a nonionic polyacrylamide, an anionic polyacrylamide (APAM) such as a polyacrylamide-co- acrylic acid, and a cationic polyacrylamide (CP AM), which can contain co-monomers such as acryloxyethyltrimethyl ammonium chloride (DAC), methacryloxyethyltrimethyl ammonium chloride (DMC), dimethyldiallyammonium chloride (DMDAAC), etc.
  • DAC acryloxyethyltrimethyl ammonium chloride
  • DMC methacryloxyethyltrimethyl ammonium chloride
  • DMDAAC dimethyldiallyammonium chloride
  • water soluble flocculating polymers useful for practicing the present disclosure include a polyamine, such as a polyamine or quaternized form thereof, e.g., polyacrylamide-co- dimethylaminoethylacrylate in quaternized form, a polyethyleneimine, a polydiallyldimethyl ammonium chloride, a polydicyandiamide, or their copolymers, a polyamide-co-amine, polyelectrolytes such as a sulfonated polystyrenes can also be used.
  • Other water soluble polymers such as polyethylene oxide and its copolymers can be used.
  • the polymer flocculants can be synthesized in the form of a variety of molecular weights (MW), electric charge types and charge density to suit specific requirements.
  • the flocculating polymer used in practicing processes of the present disclosure do not include use of activated polysaccharides or activated starches, i.e., polysaccharides and starches that have been heat treated, in sufficient amounts to lower the density of the floe to below the density of the aqueous mixture.
  • activated polysaccharides and activated starches when used in sufficiently high dosages tend to form low density floes which rise to the surface of an aqueous composition complicating removal of hydrocarbon.
  • the amount of polymer(s) used to treat hydrocarbon compositions should preferably be sufficient to flocculate solids in the composition.
  • the concentration of the one or more polymer flocculant(s) in the aqueous separating mixture has a concentration of no less than zero and up to about 0.001 wt%, e.g., no less than zero and up to about 0.005 wt%.
  • a relatively low amount of fines contained in the separated hydrocarbon can be obtained at polymer concentrations of up to about 0.01 wt%, e.g., up to about 0.04 wt%.
  • Processes of the present disclosure can also include an organic diluent to treat the hydrocarbon composition to dilute the hydrocarbon and to promote separation and recovery of the hydrocarbon.
  • Organic diluents useful for the processes of the present disclosure are soluble or mix readily with the hydrocarbon but are immiscible with water.
  • Organic diluents useful for the processes of the present disclosure aid in diluting the hydrocarbon separated from the composition and to reduce the viscosity thereof.
  • Such organic diluents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, non-aromatic hydrocarbons such as hexanes, cyclohexane, heptanes, mixtures of hydrocarbons such as naphtha, e.g., light or heavy naphtha, kerosene and paraffinic diluents, etc.
  • aromatic hydrocarbons such as benzene, toluene, xylene
  • non-aromatic hydrocarbons such as hexanes, cyclohexane, heptanes
  • mixtures of hydrocarbons such as naphtha, e.g., light or heavy naphtha, kerosene and paraffinic diluents, etc.
  • the processes of the present disclosure also can be practiced at relatively low temperatures, e.g., at ambient temperatures. Because the highly water soluble salt(s) and, optionally, polymer flocculants that are used in the process of the present disclosure are highly water soluble and effective at low temperatures, the temperature of the treated composition need not be elevated above ambient temperatures to separate hydrocarbon from the composition. In implementing processes of the present disclosure, treating the composition does not include increasing a temperature of the composition by more than 10 °C, e.g., more than 5 °C, or above ambient temperature to separate the hydrocarbon from the composition.
  • the processes of the present disclosure also can be practiced at elevated temperatures to lower the viscosity of the hydrocarbon being separated.
  • hydrocarbon such as bitumen and/or oil can be separated from the composition by treating the composition with an aqueous mixture including at least one highly water soluble salt, at least one polymer flocculant and an organic diluent at a temperature of less than 100 °C, e.g., less than 50 °C, and even less than 35 °C or less than 30 °C, to separate the hydrocarbon from the composition.
  • the treating temperature can be raised by any heating techniques including electric heating, electromagnetic heating, microwave heating, etc. Reducing the viscosity of hydrocarbon can also be carried out with the use of a diluent in treating the hydrocarbon composition thus minimizing the need for an increase in temperature to lower viscosity of the hydrocarbon.
  • Treating compositions including hydrocarbon and solids with at least one highly water soluble salt, at least one polymer flocculant and at least one organic diluent can be carried out in a number of ways.
  • treating the composition includes combining and/or mixing the various components.
  • the water soluble salt can be added directly to the composition either as an undiluted powder or as a solution;
  • the polymer flocculant can be added directly to the composition either as an undiluted material or as a solution, and the organic diluent can be added to the composition directly or with the salt and/or polymer or solutions thereof.
  • the salt and polymer can be combined in a single aqueous solution, and combined or mixed with the composition before, during or after combining or mixing the organic diluent.
  • treating the composition can include mixing or combining a stream of the composition with a stream of an aqueous mixture including the at least one highly water soluble salt and the at least one polymer flocculant and/ or mixing or combining the streams with a stream of the organic diluent.
  • the combination of streams separates the hydrocarbon from the composition.
  • the separated hydrocarbon can then be recovered as well as the aqueous mixture.
  • the separated hydrocarbon and aqueous mixture can be recovered as streams thereof form the treated composition.
  • the aqueous solution can advantageously include a significant amount of the one or more highly water soluble salt(s) and at least a portion thereof can be recovered and recycled to treat additional hydrocarbon compositions.
  • the separated aqueous mixture can include the at least one highly water soluble salt and the process can further comprise: one or more of: (i) recovering at least a portion of the separated aqueous mixture; (ii) recycling at least a portion of recovered separated aqueous mixture to treat additional hydrocarbon compositions; and/or (iii) purifying at least a portion of recovered aqueous mixture. Such purification can be carried out by reverse osmosis, for example.
  • the recovered hydrocarbon can include diluent when used to treat the composition and at least a portion of such diluent can be recovered and recycled to treat additional hydrocarbon compositions.
  • the processes of the present disclosure can be implemented in variety of hydrocarbon compositions.
  • the process of the present disclosure can be applied to oil sands such as Canadian oil sands.
  • Oil sands are a loose sand deposit which include bitumen, solids and water.
  • Oil sands can be found all over the world and are sometimes referred to as tar sands or bituminous sands.
  • Alberta Canada's oil sands include, on average, about 10 -15wt% bitumen, about 80 wt% solids and about 5 wt% water.
  • the process of the present disclosure has been described for treating hydrocarbon compositions which typically have hydrocarbon contents below about 15%, the process of the present disclosure can also be applied to mixtures including higher hydrocarbon contents, such as mixtures including over 15%, 20% 30%, 40%, 50% and higher hydrocarbon contents.
  • Such compositions can also optionally include a significant amount of water.
  • the process of the present disclosure can be applied to bitumen froth which typically contains over 40% hydrocarbon by weight, e.g., certain bitumen froth can include about 50%-60% bitumen, 30%-40% water and about 10%- 14% solids, mostly as fines.
  • pitch materials such as pitch materials from natural deposits.
  • natural deposits of Pitch Lake materials are a mixture of bitumen, minerals, water, decayed vegetation.
  • Such materials can include greater than about 50% bitumen, as high as 30% fines (mainly in the form of clays) and about 10% water as an emulsion in the composition.
  • the emulsified nature of the bitumen/water/minerals of such hydrocarbon compositions makes extraction of bitumen by conventional methods challenging.
  • Implementing processes of the present disclosure includes treating a hydrocarbon composition including a significant amount by weight of fines (>5%).
  • the compositions can include, for example, oil sands, Canadian oil sands, bitumen froth, or hydrocarbon containing by products of oil sands production, asphalt compositions and pitch materials and other natural and non- natural asphalt containing compositions, hydrocarbon contaminated solids such as hydrocarbon contaminated rock, soil, hydrocarbon waste products containing inorganic solids such as oily sludge, etc.
  • Such compositions can be treated with an aqueous mixture including at least one highly water soluble salt, at least one polymer flocculant, and at least one organic diluent to separate the hydrocarbon from the composition.
  • the hydrocarbon separated from the composition can contain a low amount of fines and/or minerals, e.g., less than about 1 wt% or no more than about 0.5 wt% or no more than about 0.1 wt%.
  • FIG. 1 is a picture of the vial showing extraction of bitumen from the oil sands with the treating mixture. Upon standing for a few minutes, a clear separation into three phases can be observed. At the bottom of the vial is the extracted sand. Between the sand and the naphtha diluted bitumen (oil) is a layer of salt solution. This layer appears optically clear. In conventional water based processes of extracting oil sands, the aqueous layer is usually cloudy because of the presence of fines and ultrafine mainly clay particles. Fines and ultrafine particles have a surface charge that severely hinders aggregation and settling of these particles. It is believed the salt solution screens these repulsive charges, facilitating aggregation. The polymer enhances aggregation and settling by binding together fines and coarse particles, which then become part of the bottom residual sands layer.
  • bitumen removed was illustrated by the infrared spectrum of the original oil sands shown in Figure 2, where it is compared to the spectrum of the extracted sand.
  • infrared light is absorbed (or scattered) at particular frequencies (usually reported as wavenumbers, cm -1 ) according to the types of chemical groups present. The height of the absorption peaks is proportional to the amount of those groups present.
  • the spectrum of the oil sands is thus a composite of bands from the oil and bands from the minerals, as shown in the top curve in Figure 2.
  • a 1% salt solution alone was used in the vial on the far left (COS-1), while next to this an aqueous solution of PAM alone (0.1% by weight) was used (COS-2), as controls.
  • COS-1 a 1% salt solution alone
  • COS-2 a 1% salt solution alone
  • the rag layer is an emulsion containing solvent-diluted bitumen, aqueous solution and minerals fines, mainly clays.
  • the second control vial which used an aqueous solution of polymer alone (0.1%) (COS-2), gave even worse results, with a very cloudy middle layer and also a significant rag layer.
  • the pilot unit included a mixing vessel, a decanting centrifuge and a stack centrifuge. The oil sands were mixed for about 10 minutes with the salt/polymer solution and naphtha, then pumped to the decanting centrifuge, where the bulk of the solids were separated from the liquids.
  • the liquids, containing a small amount of mineral fines, are then pumped to the stack centrifuge where the immiscible salt/polymer solution (plus fines) are separated from the hydrocarbons/naphtha diluted bitumen. During separation, an initially mixed product was obtained in the first minutes of operation, but equilibrium in separation was quickly achieved and a good separation achieved.
  • the recovered minerals (mainly sand and clays) appear clean and the recovered bitumen appears free of minerals and emulsified water. This was confirmed by infrared spectroscopy.
  • the spectra of the residual minerals and bitumen shown in Figure 9, show that hydrocarbon bands (near 2900 cm -1 ) were in the noise level of the baseline in the spectrum of the extracted mineral matter.
  • mineral bands in the spectrum of the recovered bitumen are beneath the detection limit. The strongest mineral bands are in the 600 cm -1 - 400 cm -1 range and are again in the noise level of the baseline. It can be seen that any mineral bands in the extracted bitumen are below the detection limit of the instrument (below about 0.1% by weight).
  • bitumen 11.4% by weight of bitumen is mixed with a seawater-polymer solution and naphtha (obtained from Sherwin Williams (VM&P naphtha).
  • the seawater was sourced from the U.S. eastern shore of the Atlantic Ocean and is believed to have a concentration of highly soluble salts of greater than 3 wt%.
  • the seawater included about 0.066 wt% of a nonionic polyacrylamide (available from SNF as FA920).
  • the proportions of oil sands to seawater solution to naphtha were 5 g to 6 g to 2.5 g, respectively (i.e., 1:1.2:0.5) in this illustrative example to allow a clear visualization of the process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La séparation d'hydrocarbures à partir de compositions comprenant des hydrocarbures et des solides tels que des sables bitumineux, des sables bitumineux par des produits, des compositions d'asphalte, etc. Le procédé comprend le traitement de telles compositions avec un mélange aqueux comprenant un sel hautement soluble dans l'eau. Le mélange peut éventuellement comprendre également un floculant polymère et/ou un diluant organique. L'hydrocarbure séparé peut être obtenu à haut rendements et faible teneur en fines solides.
PCT/US2018/059430 2017-11-08 2018-11-06 Extraction d'hydrocarbures à partir de matière particulaire WO2019094378A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120048783A1 (en) * 2009-08-24 2012-03-01 Penn State Research Foundation Analogue ionic liquids for the separation and recovery of hydrocarbons from particulate matter
CA2952136A1 (fr) * 2016-05-05 2017-11-05 Extrakt Process Solutions, Llc Traitement de residus de sables bitumineux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120048783A1 (en) * 2009-08-24 2012-03-01 Penn State Research Foundation Analogue ionic liquids for the separation and recovery of hydrocarbons from particulate matter
CA2952136A1 (fr) * 2016-05-05 2017-11-05 Extrakt Process Solutions, Llc Traitement de residus de sables bitumineux

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