US20080115935A1 - In situ conversion of heavy hydrocarbons to catalytic gas - Google Patents

In situ conversion of heavy hydrocarbons to catalytic gas Download PDF

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US20080115935A1
US20080115935A1 US11/856,566 US85656607A US2008115935A1 US 20080115935 A1 US20080115935 A1 US 20080115935A1 US 85656607 A US85656607 A US 85656607A US 2008115935 A1 US2008115935 A1 US 2008115935A1
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gas
transition metal
natural gas
catalyst
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Frank D. Mango
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Priority claimed from PCT/US2007/060215 external-priority patent/WO2007082179A2/fr
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Priority to CA2674322A priority Critical patent/CA2674322C/fr
Priority to US11/856,566 priority patent/US20080115935A1/en
Priority to PCT/US2007/078660 priority patent/WO2008085560A1/fr
Publication of US20080115935A1 publication Critical patent/US20080115935A1/en
Priority to US12/761,375 priority patent/US8091643B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • 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
    • C10G2300/1025—Natural gas
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4037—In-situ processes

Definitions

  • the present invention relates in general to the production of natural gas from high molecular weight hydrocarbons.
  • Heavy hydrocarbons such as bitumen, kerogen, Gilsonite®, and tars are high molecular weight hydrocarbons frequently encountered in subterranean formations. These hydrocarbons range from thick viscous liquids to solids at ambient temperatures and are generally quite expensive to recover in useful form.
  • Bitumen occurs naturally in tar sands in locations such as Alberta, Canada and in the Orinoco oil belt north of the Orinoco river in Venezuela.
  • Kerogens are the precursors to fossil fuels, and are also the material that forms oil shales. Kerogens, believed to be the precursor to bitumens, are frequently found in sedimentary rock formations.
  • Heavy hydrocarbons in general have been used in a number of applications such as in asphalt and tar compositions for paving roads and roofing applications and as an ingredient in waterproofing formulations. Importantly, they are a potentially valuable feedstock for generating lighter hydrocarbons. This is typically accomplished by thermal cracking and hydrogenolysis processes, for example.
  • the present invention relates to a method for the catalytic conversion of heavy hydrocarbons to natural gas.
  • a method of producing natural gas from a heavy hydrocarbon-containing subterranean formation includes: placing a catalyst comprising at least one transition metal into the formation, injecting a stimulation gas containing less than 1 ppm oxygen (hereafter referred to as ‘anoxic’) into the formation, and collecting the natural gas generated in the formation.
  • anoxic a stimulation gas containing less than 1 ppm oxygen
  • a method of producing natural gas from heavy hydrocarbons includes: providing a mixture of heavy hydrocarbons and a catalyst that includes at least one transition metal, adding an anoxic stimulation gas to the mixture, and heating the mixture in the presence of the stimulation gas.
  • a method of forming natural gas includes: providing a mixture of heavy hydrocarbons and a catalyst having at least one transition metal; adding an anoxic stimulation gas to the mixture, and heating the mixture in the presence of the stimulation gas
  • FIG. 1 is a plot showing the generation of methane and ethane over time from Barnett Shale in flowing helium at 250° C.
  • FIG. 2 is a plot showing the generation of methane and ethane over time from Monterey source rock KG-4 in flowing helium at 250° C.
  • FIG. 3 a is a plot showing gas chromatographic analyses of the amount and types of gasses produced from a sample of New Albany shale subject to an isothermal helium flow, at 100° C. and 350° C. under anoxic helium flow.
  • FIG. 3 b is a plot showing gas chromatographic analyses of the amount and types of gasses produced from a sample of New Albany shale subject to a flow of helium with 10 ppm O 2 at 100° C. and 350° C.
  • FIG. 4 is a plot showing gaseous hydrocarbon evolution over 21.7 hours at 50° C. from a sample of shale from Black Warrior Basin.
  • Embodiments disclosed herein are directed to a method in which various transition metal-containing catalysts present as zero- or low-valent metal complexes, are co-injected with sand or other proppant into reservoirs rocks under sufficiently high pressures to fracture the rocks thus creating conduits of porous sand through which the transition metal complexes can pass into the regions of the formation containing heavy hydrocarbon materials.
  • the catalysts may be delivered to hydrocarbon-containing sites within a formation using muds.
  • a method of producing natural gas from a heavy hydrocarbon-containing subterranean formation includes placing a catalyst which has at least one transition metal into the formation, injecting an anoxic stimulation gas into the formation (in some embodiments simultaneous with catalyst introduction), and collecting the natural gas generated in the formation.
  • Heavy Hydrocarbons as used herein include, but is not limited to all forms of carbonaceous deposits with sufficient hydrogen to convert to natural gas: (—CHx—) ⁇ gas+(—CHy—) where x>y. Examples include kerogens, solid hydrocarbons (Gilsonite, tars and the like), and bitumens. Such heavy hydrocarbons may be processed in situ in a formation. Alternatively, any of the hydrocarbons may also be reacted outside the context of a subterranean location, for example, in a batch reactor under carefully controlled conditions. Such conditions would include, for example, the substantial removal of oxygen which is prone to poisoning transition metal catalysts.
  • Typical source rocks usually shales or limestones, contain about 1% organic matter, although a rich source rock might have as much as 20%.
  • Source rocks convert their bitumen to natural gas at moderate temperatures (25 to 200° C.) in their natural state without hydrogen addition (see Experimental examples below). They do so chaotically, with random bursts of activity within periods of little or no activity, a phenomenon not uncommon in transition metal catalysis. Such behavior has been observed in a number of hydrogenation reactions including the hydrogenation of carbon monoxide, ethylene, and nitric oxide over Ni, Pt, Pd, Ir, Rh, and Ag (Eiswirth, M., 1993. Chaos in surface-catalyzed reactions. Ch.
  • the method of converting heavy hydrocarbons to natural gas may be accelerated in situ by injecting transition metals into reservoir rocks.
  • the catalyst components may be obtained from an active source rock by isolation of the transition metals from active source rock.
  • the source rock itself may be used without isolation of the individual active transition metals by generating a fine powder form of the source rock.
  • high catalytic activity may be achieved by having catalyst particles with large surface area to volume ratios.
  • it may be particularly beneficial to mill the source rock to very small particle size, for example, 10 nm-10,000 nm average diameter, though larger particles may be used as well.
  • purified reagent grade transition metal components may be used and mixed in appropriate concentrations to reflect the naturally occurring compositions.
  • active source rocks may contain sufficient low-valent transition metals (100 to 10,000 ppb) to promote the reaction at reservoir temperatures (100° C. to 200+° C.) on a production time scale (days to years).
  • Source rock activities may be determined experimentally in flowing helium at various temperatures. An assay procedure has been described by Mango (U.S. Pat. No. 7,153,688).
  • the transition metal may be a zero-valent transition metal, a low-valent transition metal, alloys, and mixtures thereof. Any transition metal that serves as a hydrogenation catalyst may be viable as a catalyst for the disproportionation reaction of heavy hydrocarbons.
  • Various transition metals catalyze the hydrogenolysis of hydrocarbons to gas (Somorjai, G. A., 1994. Introduction to Surface Chemistry and Catalysis. John Wiley & Sons, New York. pg. 526); for example, C 2 H 6 +H 2 ⁇ 2 CH 4 . It has also been demonstrated that source rocks are catalytic in the hydrogenolysis of hydrocarbons (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.
  • Active source rock may include transition metals such as molybdenum, nickel, cobalt, iron, copper, palladium, platinum, rhodium, ruthenium, tungsten, rhenium, osmium, and iridium.
  • the catalyst components may be immobilized and introduced into the formation on a proppant, in some embodiments.
  • catalysts may be injected as gases, metal carbonyls, for example, which could dissolve in the carbonaceous sediments, decompose with time, thus delivering to the sediments low-valent active metals such as Ni, Co, Fe.
  • the catalyst may be introduced at various stages in oil-based muds, for example. Fine metal particles could also be injected directly with sand in reservoir fracturing, thus dispersing fine particles of active catalyst throughout the network of porous sand conduits that carry hydrocarbons from the reservoir to the surface.
  • Catalysts may be coated with paraffins (C 8 to C 18 ) to protect them from oxygen-poisoning while on the surface and during injection into the reservoir.
  • Stimulation gas Since active metals in natural sedimentary rocks are poisoned irreversibly by oxygen (U.S. Pat. No. 7,153,688), it is beneficial that the stimulation be anoxic ( ⁇ 1 ppm O 2 ). Trace amounts of oxygen picked up in processing can be easily and inexpensively removed with commercial oxygen scrubbers.
  • the stimulation gas may include natural gas, gas depleted of methane, carbon dioxide, helium, argon, and nitrogen.
  • hydrogen gas may interfere with separation and therefore is not an ideal stimulation gas.
  • the stimulation gas may also be used not only for the fracturing, but also as a means of depositing the catalyst within the formation.
  • the stimulation of catalytic gas generation from bitumen in reservoir rocks may be achieved through a single well bore in a permeable reservoirs by injecting and withdrawing gas sequentially to create sufficient turbulence to stimulate chaotic gas generation or it may be achieved through multiple injection wells positioned to maximize continuous gas flow through the permeable reservoir to production wells that collect the injected gas plus catalytic gas. Production units would collect produced gas, injecting a fraction to maintain a continuous process and sending the remainder to market.
  • Fracturing the reservoir may be beneficial. Fracturing may be accomplished with injected sand or other appropriate proppant to create interlacing conduits of porous sand to carry injected gas through the reservoir to conduits of porous sands that carry the injected gas plus catalytic gas from the reservoir to production units.
  • the flowing gas injected into the reservoir stimulates catalytic activity within the shale.
  • Fracturing may also be used to expose active catalytic sites inherent in shales and other heavy hydrocarbon-containing formations. Care should be taken in the fracturing process to minimize the exposure of these freshly exposed catalytic sites to oxygen and other oxidants that may deactivate low valent transition metal catalysts. Elemental oxygen in excess of 1 ppm can reduce the effectiveness of the catalytic reaction with heavy hydrocarbons. It has been observed, however, that this poisoning of catalytic activity is temperature sensitive. At temperatures lower than about 50° C. catalytic activity may be unaffected by the presence of oxygen, for example. For the common fracturing fluid water, a simple degassing procedure prior to fracturing may be sufficient to protect the nascent catalytic sites exposed during fracturing. In order to establish natural gas production after fracturing, the stimulation gas is simply allowed to flow over the newly fractured formation.
  • Injected gas may be natural gas produced from the deposit or natural gas produced from another deposit elsewhere.
  • the process could be carried out by sequential injections where the reservoir is pressured, then allowed to stand and exhaust its induced pressure over time. This process could be repeated multiple times until the reservoir was exhausted of heavy hydrocarbons.
  • the process could also be carried out in a continuous mode where gas is injected continuously into one well and withdrawn continuously from another.
  • the two wells (or multiple wells) would be interconnected through a production unit that withdraws produced gas from the system sending excess gas to market and re-injecting the remainder to sustain continuous production.
  • Heavy hydrocarbon to natural gas In addition to methods for in situ cracking of heavy hydrocarbons in a subterranean location, one may also produce natural gas from isolated heavy hydrocarbons in batch reactors, for example. To carry out such production the method entails mixing isolated heavy hydrocarbons (for example mined bitumen) with an active catalyst as described above. An anoxic stimulation gas may be introduced and the mixture heated under anoxic conditions.
  • the catalyst may be an active source rock ground into fine powder as described above.
  • the active transition metal components may be isolated from the source rock or stock mixtures prepared from commercially available sources in proportions identified in high activity source rock.
  • the stimulation gas may be natural gas, natural gas depleted of methane, carbon dioxide, helium, argon, and nitrogen. In the context of batch reaction, such a stimulation gas may be provided as a flow while heating the bitumen catalyst mixture. Catalytic activity may be facilitated by heating in a range from about 25° C. to about 350° C. and from about 25° C. to about 250° C. in other embodiments. In particular embodiments, heating may be carried out in a range from about 100° C. to about 200° C. In all embodiments, it is beneficial that the stimulation gas be anoxic ( ⁇ 1 pp O 2 ).
  • Methods disclosed herein may be used in the production of natural gas (catalytic gas).
  • the aforementioned method for the disproportionation of bitumen and high molecular weight hydrocarbons may be used in such production. This may be carried out in batch reactors, or generated directly from tar sand sources where it may be collected in the field and distributed commercially.
  • the first methane peak (presumably adsorbed and catalytic methane from the 10 min purge at 350° C.) emerged at 12.5 min (5.8 ⁇ 10 ⁇ 5 g CH 4 ) followed by a flat baseline over the next 20 min showing that the sample was no longer releasing methane.
  • Three sharp peaks of increasing intensity then appeared at 45 min. (9.9 ⁇ 10 ⁇ 6 g CH 4 ), 68 min. (1.6 ⁇ 10 ⁇ 5 g CH 4 ), and 94 min. (5.6 ⁇ 10 ⁇ 5 g CH 4 ).
  • the final three peaks constitute 2.2 ⁇ 10 ⁇ 2 mg CH 4 /(g rock hr) which is greater than that for this rock under our usual conditions (in hydrogen) (5.7 ⁇ 10 ⁇ 3 mg CH 4 /(g rock hr).
  • a Monterey shale (Miocene, Calif.) sample generates methane at a rate of ⁇ 6 ⁇ 10 ⁇ 6 g C 1 /(g rock hr) in hydrogen gas containing 3% propane under closed conditions (30 minutes) at 250° C. and generates very little methane at 200° C. under the same conditions (30 minutes). Under flowing helium at 200° C., the same rock converts its bitumen to gas at a rate of 1.3 ⁇ 10 ⁇ 4 g C 1 /(g rock hr).
  • mass-transfer stimulation gas may achieve two positive effects: 1) it transports hydrocarbons from heavy hydrocarbon deposits to active catalytic sites, and 2) it removes activity-suppressing agents (products' and adsorbents) from the active sites catalyst surfaces.
  • Marine shales generate two distinct gases in the laboratory, one at high temperatures (>300° C.) from kerogen cracking, and the other at low temperatures ( ⁇ 100° C.) through the catalytic action of low-valent transition metals as shown in exemplary FIGS. 3 a and 3 b .
  • the data in FIGS. 3 a and 3 b were obtained from a sample of New Albany shale subject to an isothermal helium flow, at 100° C. and 350° C., sequentially.
  • FIG. 3 a shows the system under an anoxic helium flow.
  • FIG. 3 b shows the system with a flow of helium with 10 ppm O 2 .
  • New Albany shale generates catalytic gas dominated by propane.
  • the high-propane peaks at 100 and 350° C. are catalytic gas peaks.
  • Thermal gas from kerogen cracking is represented by the methane peak (500 ppm vol) at 350° C.
  • Catalytic gas is 90% of the total gas in FIG. 3 a.
  • Low-temperature gas forms at temperatures comparable to geological reservoir temperatures, but only when there is gas flow under anoxic conditions. This is achieved in the laboratory by grinding the shales in pure argon to expose inner anoxic surfaces, and then passing purified helium over the surfaces at constant temperature.
  • a Paleozoic marine shale Chattanooga/Floyd
  • Black Warrior Basin Alabama/Mississippi
  • the methods describe herein provide a means for recovery useful catalytic gas from heavy hydrocarbons in situ from subterranean formations.
  • the conversion of heavy hydrocarbon extends the useful lifetime of reservoir enhancing the oil recovery process.
  • the same process may be duplicated under controlled conditions in batch reactors for commercial production of natural gas.
  • the availability of certain heavy hydrocarbons, such as bitumen, from renewable resources may provide an environmentally sound means for natural gas production.

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CA2674322A CA2674322C (fr) 2007-01-08 2007-09-17 Conversion in situ d'hydrocarbures lourds en gaz catalytique
US11/856,566 US20080115935A1 (en) 2006-01-06 2007-09-17 In situ conversion of heavy hydrocarbons to catalytic gas
PCT/US2007/078660 WO2008085560A1 (fr) 2007-01-08 2007-09-17 Conversion in situ d'hydrocarbures lourds en gaz catalytique
US12/761,375 US8091643B2 (en) 2006-01-06 2010-04-15 In situ conversion of heavy hydrocarbons to catalytic gas

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Cited By (6)

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US20070199698A1 (en) * 2006-02-27 2007-08-30 Grant Hocking Enhanced Hydrocarbon Recovery By Steam Injection of Oil Sand Formations
US20090145606A1 (en) * 2006-02-27 2009-06-11 Grant Hocking Enhanced Hydrocarbon Recovery By Steam Injection of Oil Sand FOrmations
US20110077445A1 (en) * 2006-01-06 2011-03-31 Mango Frank D Generating natural gas from heavy hydrocarbons
WO2011140286A2 (fr) * 2010-05-04 2011-11-10 Petroleum Habitats, L.L.C. Procédés et appareil favorisant la production d'hydrocarbures générés par catalyse
US20130161008A1 (en) * 2011-12-22 2013-06-27 Argonne National Laboratory Preparation and use of nano-catalysts for in-situ reaction with kerogen
US8727006B2 (en) 2010-05-04 2014-05-20 Petroleum Habitats, Llc Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations

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CA2822659A1 (fr) 2010-12-22 2012-06-28 Chevron U.S.A. Inc. Conversion et recuperation de kerogene in situ
US8701788B2 (en) 2011-12-22 2014-04-22 Chevron U.S.A. Inc. Preconditioning a subsurface shale formation by removing extractible organics
US8851177B2 (en) 2011-12-22 2014-10-07 Chevron U.S.A. Inc. In-situ kerogen conversion and oxidant regeneration
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