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WO2008043785A1 - Procédé en deux étapes pour la conversion de sable bitumeux en combustibles liquides et produits chimiques de spécialité - Google Patents

Procédé en deux étapes pour la conversion de sable bitumeux en combustibles liquides et produits chimiques de spécialité Download PDF

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Publication number
WO2008043785A1
WO2008043785A1 PCT/EP2007/060766 EP2007060766W WO2008043785A1 WO 2008043785 A1 WO2008043785 A1 WO 2008043785A1 EP 2007060766 W EP2007060766 W EP 2007060766W WO 2008043785 A1 WO2008043785 A1 WO 2008043785A1
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WO
WIPO (PCT)
Prior art keywords
tar sand
conversion
unconverted
activated
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2007/060766
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English (en)
Inventor
Paul O'connor
Dennis Stamires
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bioecon International Holding NV
Original Assignee
Bioecon International Holding NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bioecon International Holding NV filed Critical Bioecon International Holding NV
Priority to CA002665792A priority Critical patent/CA2665792A1/fr
Priority to US12/444,862 priority patent/US20100133149A1/en
Publication of WO2008043785A1 publication Critical patent/WO2008043785A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08

Definitions

  • the present invention relates to the conversion of hydrogen-poor fluid hydrocarbons to liquid fuels and specialty chemicals.
  • Hydrogen-poor fluid hydrocarbons are characterized by a high viscosity, which makes them difficult to process. It is desirable to develop processes that are able to process these hydrocarbons without requiring expensive equipment or demanding processing conditions in terms of temperature and pressure.
  • Ti Sand means hydrogen-poor fluid hydrocarbon materials, and encompasses tar sand per se, oil sand, oil shale, heavy crude oil, bottoms from refinery processes, and the like. In general, these materials contain less than 15% hydrogen, often only about 10% hydrogen.
  • the present invention relates to a process for converting Tar Sand to a liquid fuel comprising the steps of: a) activating the Tar Sand to make it more susceptible to conversion; b) optionally, adding a solvent; c) partially converting the activated Tar Sand to form solubiiized material; d) subjecting unconverted Tar Sand from step c) to a conversion process.
  • step c) Due to the activation taking place in step a), optionally aided by the addition of a solvent (step b), step c) can be carried out under mild conditions. As a result the product obtained in step c) is not substantially degraded. Unconverted Tar Sand from step c) is subsequently subjected to a second conversion in step d). Optionally, and preferably, converted Tar Sand obtained in step c) is removed from the unconverted Tar Sand before the latter is subjected to a second conversion in step d). if conversion products from step c) are first removed, step d) may be carried out under more severe conditions than step c). In the alternative, step d) may be preceded by a second activation step so that the unconverted Tar Sand is more susceptible to the conversion process of step d).
  • Figure 1 is a schematic diagram of an embodiment of the process of the present invention.
  • FIG. 2 is a schematic diagram of an alternate embodiment of the process of the present invention.
  • the present invention relates to a process for converting Tar Sand to a liquid fuel comprising the steps of: a) activating the Tar Sand to make it more susceptible to conversion; b) optionally, adding a solvent; c) partially converting the activated Tar Sand to form soiubilized material; d) subjecting unconverted Tar Sand from step c) to a conversion process.
  • the process provides the general advantage of requiring less severe process conditions than, for example, traditional HTU or pyrolysis processes. Accordingly, the process is more cost-effective and requires simpler less expensive equipment. The process is also environmentally more acceptable, and produces product of higher quality, and more suitable for conversion to fuels and chemicals.
  • Particular embodiments of the process provide homogenous, intimate mixtures of Tar Sand materia! with a solvent and/or a solid and/or a liquid additive, which provides advantages for subsequent conversion.
  • One important aspect of the process of the present invention is that it removes easily converted components of the Tar Sand material from the reaction mixture after a first conversion, allowing other, more difficultly converted components to be subjected to somewhat more severe conversion conditions without exposing the products already obtained to undesired degradation.
  • Step a) of the process generally involves providing an intimate mixture of the Tar Sand with a solvent, a particulate solid and/or liquid material, or both a solvent and a particulate solid material. If the material is an oil shale it is desirable to reduce the particle size of the Tar Sand by processes such as milling, grinding, and the like.
  • the mixing step may be combined with the process of reducing the particle size of the Tar Sand material.
  • ball milling or grinding of the Tar Sand in the presence of a particulate solid material will result in an intimate mixture of the Tar Sand and the particulate solid material.
  • the pressure inside the extruder is determined by the viscosity of the mass within the extruder, the design of the screw within the extruder (for example, a tapered pitch screw provides a higher pressure than a constant pitch screw), and the design of the perforated plate at the outlet of the extruder.
  • the back pressure provided by this plate is a function of the amount of open area in relation to the amount of closed area, with lower open area/closed area ratios providing greater back pressure.
  • two or more extruders may be provided in series, or the material may be subjected to two or more passes through one extruder. Similarly, the capacity of a plant may be readily increased by operating two or more extruders in parallel.
  • Suitable solvents for use in step b) include water, alcohols ⁇ in particular ethanol and glycerol), bio-oil or other products from the subsequent conversion of the Tar Sand, liquid acids, aqueous solutions of acids and bases, liquid CO 2 , and the like.
  • Water is the preferred solvent in most applications, because of its availability, low cost, and ease of handling. Liquids that are produced during the subsequent conversion of the Tar Sand are also readily available and may be preferred for that reason.
  • Suitable solid materials for use in step a) include solid acids and bases, salts, minerals, clays, layered materials, and the like. Solid materiais having catalytic properties are preferred. Examples include metal oxides, metal hydroxides, alkaline and alkaline earth oxides, hydroxides, carbonates, hydroxyl carbonates, hyd rota I cite-like materials, etc. As has been noted earlier, it may be desirable to add several solid materials to the Tar Sand, or a combination of one or more solid materials and one or more solvents.
  • inorganic solids may precipitate from solution in response to an increase in temperature or a change in pH.
  • An increase in temperature may be effected in the kneader by heating the barrel, or by injecting steam.
  • a pH change may be effected by injecting a solution of an acid or a base.
  • amorphous materials may be caused to crystallize by increasing the temperature of the mixture.
  • Tar Sand contains sufficient quantities of water for the present purpose, obviating the need for adding additional solvent. It may even be desirable to remove water during the activation step. This may for example be accomplished by heating the Tar Sand to a temperature above 100 0 C, and letting off steam via pressure valves located along the barrel of the extrude, if an extruder is used in the process.
  • conversion step c) commences while the activated Tar Sand is still being processed in the kneader or extruder or in both. If this process is not completed in the kneader, the activated Tar Sand may be processed further in a second kneader, or it may be subjected to a second pass through the first kneader. Alternatively, the Tar Sand may be transferred to a different processor to complete step c).
  • a suitable example of such a processor is a filter press, which can be operated at desirable conditions of temperature and pressure.
  • liquid products resulting from conversion step c) be separated from unconverted Tar Sand.
  • the purpose of this separation is twofold. Firstly, it reduces the mass of materia! that needs to be subjected to further conversion in step d), which makes the operation of step d) more efficient. Secondly, it avoids subjecting liquid conversion products from step c) to the subsequent conversion process, avoiding a degradation of this liquid product by such further processing.
  • part of the first conversion takes place in a filter press under conditions of increased temperature and pressure. This may be accomplished by loading the activated Tar Sand into a filter press, and injecting steam to increase both the temperature and the pressure.
  • the filter press is de-pressurized over a filter medium, such as a filter cloth or screen, and the reaction product is separated into a liquid filtrate stream and a filter cake.
  • the liquid stream comprises solvent and liquid conversion product, as well as fine particles of unconverted Tar Sand.
  • the filter cake comprises unconverted Tar Sand, retained solvent, and liquid reaction product.
  • unconverted Tar Sand refers to Tar Sand that has not been converted to a liquid product in step c).
  • the term includes Tar Sand material that has not undergone any chemical conversion.
  • the term also includes Tar Sand that has undergone some conversion, but insufficient to form a liquid.
  • hydrocarbons may have been converted to hydrocarbons of a lower average molecular weight, but still be semi-solid. This would be considered “unconverted Tar Sand” within the meaning of this term as used herein.
  • Such a material may well be an "activated unconverted Tar Sand” if its molecular weight is reduced and/or its macro and/or micro structure has changed, in a way that makes it more susceptible for conversion to a liquid product in step d).
  • the liquid may be separated from remaining solids by nano- filtration or membrane separation.
  • an extractive separation may be used.
  • the unconverted Tar Sand is subjected to a second conversion process in step d). If the liquid conversion product of step c) is removed from the unconverted Tar Sand prior to step d), this second conversion may be carried out under more severe conditions than the first conversion, without risking degradation of reaction products already formed.
  • the unconverted Tar Sand may be subjected to a conventional HTU or pyrolysis process.
  • the unconverted Tar Sand is activated prior to step d) so that step d) may be carried out under less severe conditions than the prior art HTU and pyrolysis processes.
  • the unconverted Tar Sand from step c) is already activated, for example because inorganic particulate materials added in step a) are carried over with the unconverted Tar Sand into step d).
  • the unconverted Tar Sand may also be activated as a result of a partial conversion in step c), insufficient to render the Tar Sand liquid, but sufficient to make it more susceptible to further conversion.
  • step d Any conversion process is suitable for use in step d).
  • HTU and pyrolysis have already been mentioned; desirably, these processes are conducted under conditions as mild as the activation of the Tar Sand will permit.
  • Gasification may be a desirable option, for example to create gaseous fuel for meeting the heat requirements of the overall process.
  • both steps c) and d) produce a mixture of liquid hydrocarbons, which may be converted to suitable liquid transportation fuels in modified refinery processes such as fluid catalytic cracking, hydroconversion, thermal conversion, and the like.
  • the Tar Sand derived liquid hydrocarbons may be the sole feedstock, or they may be blended with conventional, crude oil-based feedstocks.
  • the activation step a) is conducted in a kneader/extruder assembly in the presence of an inorganic solid, for example an alkaline or alkaline earth metal oxide or hydroxide, and the product of step c) is hydrothermaiiy treated in step d).
  • an inorganic solid for example an alkaline or alkaline earth metal oxide or hydroxide
  • the product of step c) is hydrothermaiiy treated in step d).
  • the inorganic material which is homogenously mixed in step a) / step b) is thus most effectively dispersed and present in steps c) and/or d) in intimate contact with the unconverted Tar Sand, resulting in an efficient conversion.
  • Said solids may possess catalytic properties that further enhance the conversion process.
  • the inorganic additive introduced in step a) may be simply a heat transferring medium, like for example sand, clay or a mineral, ore or soil, which may have also catalytic properties.
  • the product of step c) can be subjected to a pyrolysis conversion process. The advantage of this process is that here the heat transfer medium is in close and intimate contact with the Tar Sand in a dispersed form.
  • the activation in step a) may involve the addition of an acid or a base, which, aided by the application of heat and/or steam, will break down the compact structure of the Tar Sand composite, rendering it more susceptible to a subsequent conversion, for example by acid hydrolysis and/or enzymatic conversion.
  • the Tar Sand in step a) containing water and optionally an additive is heated above 100 0 C, while being mechanically treated, so that the water is allowed to evaporate.
  • the Tar Sand is mechanically processed in the presence of other carbonaceous materials such as coal, lignite, and biomass in step a) and step b) optionally with the addition of additives, followed by gasification of the unconverted materiais,
  • the Tar Sand is intimately mixed with an additive in a ball mill, grinding the components together to form the activated Tar Sand.
  • a liquid solvent can be added.
  • the Tar Sand is grinded with an additive in a fluidized and/or spouted bed, as disclosed in US60/831 ,220, the disclosures of which are incorporated herein by reference.
  • a liquid solvent can be added.
  • the unconverted Tar Sand of step c) is converted to paraffins suitable for diesel fuels.
  • the unconverted Tar Sand of step c) which often appears to be the fibrous crystalline cellulose coated with an additive, is converted to materials suitable for paper, board or construction materials
  • the unconverted materia! (mainly crystalline cellulose) is converted to a transportation fuel by aqueous phase reforming as suggested by Huber et a!., see: G.W. Huber, J.N. Chheda, CJ. Barrett, J.A. Dumesic, Science 308 (2005) 1446.
  • the solubilized material is converted to a transportation fue! by aqueous phase reforming as suggested by Huber et a!., see: G.W. Huber, J.N. Chheda, CJ. Barrett, J.A. Dumesic, Science 308 (2005) 1446.
  • the unconverted material of step b and/or c) is first submitted to electromagnetic and/or ultrasound energy, optionally in the presence of a polar solvent such as ethanol. Following this treatment the so activated material is converted by any of the above means.
  • the unconverted material of step b and/or c), which comprises a material susceptible to the absorption of electro-magnetic radiation is first submitted to electromagnetic optionally in the presence of a polar solvent such as ethanol. Following this treatment the so activated material is converted by any of the above means.
  • the unconverted material of step b and/or c) is first submitted to intimate mixing with an additive, optionally in the presence of a solvent such as ethanol. Following this treatment the so activated material is converted by any of the above means.
  • Figure 1 shows one particular embodiment 100 of the process of the present invention.
  • Tar Sand 101 and catalyst 102 are mixed in mechanical mixer 110, with the optional addition of solvent 103.
  • After mixing the mixture is transferred to a first reactor 120, for a first, partial, conversion step. This conversion step is carried out under mild conditions.
  • reaction product 106 is separated from the mixture, and removed for further processing. The removal of reaction product 106 ensures that reaction product 106 is not subjected to the subsequent, more severe conversion in reactor 140.
  • the unconverted portion 131 of the mixture is transferred to a second conversion reactor 140, where it is subjected to a more severe conversion reaction.
  • additional catalyst 107 is added at this stage.
  • solvent 108 may be added.
  • reaction product 109 is recovered from reactor 140.
  • Figure 2 shows an alternate embodiment 200 of the process of the present invention.
  • Tar Sand 201 and catalyst 202 are mixed in mechanical mixer 210, with the optional addition of solvent 203. After mixing the mixture is transferred to a first reactor 220, for a first, partial, conversion step. This conversion step is carried out under mild conditions.
  • reaction product 206 is separated from the mixture, and removed for further processing. The removal of reaction product 206 ensures that reaction product 206 is not subjected to the subsequent, more severe conversion in reactor 240.
  • the unconverted portion 231 of the mixture is transferred to a second conversion reactor 240, where it is subjected to a more severe conversion reaction.
  • additional catalyst 207 is added at this stage.
  • solvent 208 may be added.
  • Reaction product 209 is recovered from reactor 240, and combined with reaction product 206 for further processing in refinery process 250.
  • Process 250 may comprise any number of conventional refinery processes, such as fluid catalytic cracking (FCC), hyrotreatment processing (HTP), thermal cracking (TC), and the like.
  • FCC fluid catalytic cracking
  • HTP hyrotreatment processing
  • TC thermal cracking

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

Abstract

L'invention concerne un procédé de conversion de sable bitumineux en combustibles et/ou en produits chimiques de valeur. Le procédé comporte les étapes consistant à a) activer le sable bitumineux pour le rendre plus sensible à une conversion; c) convertir partiellement le sable bitumineux en un matériau solubilisé; et d) soumettre le sable bitumineux non converti à une seconde étape de conversion. Le procédé comporte facultativement une étape b) d'addition d'un solvant au sable bitumineux activé. Dans un mode de réalisation préféré, le sable bitumineux solubilisé obtenu à l'étape c) est retiré avant que le sable bitumineux non converti ne soit soumis à l'étape d).
PCT/EP2007/060766 2006-10-10 2007-10-10 Procédé en deux étapes pour la conversion de sable bitumeux en combustibles liquides et produits chimiques de spécialité Ceased WO2008043785A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002665792A CA2665792A1 (fr) 2006-10-10 2007-10-10 Procede en deux etapes pour la conversion de sable bitumeux en combustibles liquides et produits chimiques de specialite
US12/444,862 US20100133149A1 (en) 2006-10-10 2007-10-10 Two-stage process for the conversion of tar sand to liquid fuels and specialty chemicals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US85025706P 2006-10-10 2006-10-10
US60/850,257 2006-10-10

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WO2008043785A1 true WO2008043785A1 (fr) 2008-04-17

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CA (1) CA2665792A1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2228422A1 (fr) * 2009-03-11 2010-09-15 D. Kanbier Récupération sèche de l'huile à partir de sables bitumineux Athabasca

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9375725B2 (en) 2010-12-03 2016-06-28 Bepex International, Llc System and method for the treatment of oil sands
CA2729457C (fr) 2011-01-27 2013-08-06 Fort Hills Energy L.P. Procede pour l'integration d'un centre de traitement de l'ecume paraffinique a une installation de forage et d'extraction de minerai bitumineux
CA2906715C (fr) 2011-02-25 2016-07-26 Fort Hills Energy L.P. Procede de traitement de bitume dilue a forte teneur en paraffine
CA2931815C (fr) 2011-03-01 2020-10-27 Fort Hills Energy L.P. Procede et unite pour la recuperation de solvant dans des residus dilues dans un solvant, provenant du traitement de la mousse de bitume
CA2806891C (fr) 2011-03-04 2014-12-09 Fort Hills Energy L.P. Procede de traitement a solvant pour le traitement de mousse de bitume a l'aide de la distribution axisymetrique d'alimentation de separateur
CA2735311C (fr) 2011-03-22 2013-09-24 Fort Hills Energy L.P. Procede pour un chauffage a injection de vapeur directe de la mousse de bitume des sables bitumineux
CA2737410C (fr) 2011-04-15 2013-10-15 Fort Hills Energy L.P. Dispositif de recuperation de chaleur pour integration dans une usine de traitement de mousse de bitume avec circuit de refroidissement en boucle fermee
CA2738700C (fr) 2011-04-28 2013-11-19 Fort Hills Energy L.P. Ursr avec configurations de pulverisation d'admission pour la distribution des residus dilues par solvant
CA2857718C (fr) 2011-05-04 2015-07-07 Fort Hills Energy L.P. Procede de regulation de debit pour les operations de traitement de la mousse de bitume
CA2832269C (fr) 2011-05-18 2017-10-17 Fort Hills Energy L.P. Regulation de temperature pour un procede de traitement de mousse de bitume avec chauffage de compensation de courants de solvant

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CA2665792A1 (fr) 2008-04-17
US20100133149A1 (en) 2010-06-03

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