US20060231455A1 - Method for production and upgrading of oil - Google Patents

Method for production and upgrading of oil Download PDF

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US20060231455A1
US20060231455A1 US10/563,991 US56399104A US2006231455A1 US 20060231455 A1 US20060231455 A1 US 20060231455A1 US 56399104 A US56399104 A US 56399104A US 2006231455 A1 US2006231455 A1 US 2006231455A1
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heavy
oil
reforming
process according
heavy oil
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Ola Olsvik
Kjell Moljord
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Equinor ASA
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Statoil ASA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
    • F25J3/04569—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for enhanced or tertiary oil recovery
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/164—Injecting CO2 or carbonated water
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/166—Injecting a gaseous medium; Injecting a gaseous medium and a liquid medium
    • E21B43/168—Injecting a gaseous medium
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/243—Combustion in situ
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J3/04012—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling
    • F25J3/04018—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling of main feed air
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04109—Arrangements of compressors and /or their drivers
    • F25J3/04115—Arrangements of compressors and /or their drivers characterised by the type of prime driver, e.g. hot gas expander
    • F25J3/04121—Steam turbine as the prime mechanical driver
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
    • F25J3/04539—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/063—Refinery processes
    • C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P90/70—Combining sequestration of CO2 and exploitation of hydrocarbons by injecting CO2 or carbonated water in oil wells

Definitions

  • the present invention relates to an enviromnental-friendly, integrated process for increased production and upgrading/refining of heavy and extra-heavy crude oil to finished products, based on extensive use of hydrogen to maximise the yield of liquid products, while cogenerating large amounts of steam, CO 2 and optionally N 2 produced by large-scale natural gas conversion, used for increased oil production.
  • the finished products from upgrading/refining of heavy/extra heavy oils will be predominantly naphtha, kerosene, diesel and fuel oil, shipped separately or blended.
  • the upgrader is usually designed for the specific heavy oil in question, while the synthetic crude with API in the range of typically 20-35 API is an attractive feedstock for conventional refineries, within certain limitations.
  • the essential feature of the heavy/extra heavy oil upgrader will be the conversion of residue, either by carbon rejection or hydrogen addition, to give a stable synthetic crude that might be more or less residue-free, while the liquid fractions do not have the quality needed for road transportation fuels.
  • a subsequent refining of the synthetic crude is needed to produce finished products with the right quality, but this reprocessing is not very energy efficient since the synthetic crude oil has to be reheated and fractionated.
  • the heavy oils generally have high density and high viscosity due to the large presence of higher boiling, polyaromatic molecules in which the resin and asphaltene content can be as high as 70%.
  • these oils are low in hydrogen content, such as for Athabasca bitumen with an ratio (atomic) H/C equal to 1.49, compared to conventional crudes with a ratio H/C typically around 1.8, which is slightly lower than the value of the most important refinery products, gasoline and diesel (see, J. S. Speight: “The chemistry and technology of petroleum”, 3rd ed., Marcel Dekker, Inc., New York, 1999).
  • natural gas is rich in hydrogen with a H/C-ratio around 3.8; therefore natural gas represents a natural source of hydrogen for upgrading of heavy oil, as it is when refineries need additional hydrogen to close their hydrogen balance.
  • the attractiveness of using natural gas as hydrogen source will depend on local factors such as availability and cost of the natural gas.
  • the need for hydrogen in the refineries depends on the feedstock and product slates, as well as the specific refinery configuration.
  • the general market trend is towards lighter products such as LPG, naphtha, gasoline and diesel, putting a pressure on the refineries with respect to upgrading of the heavier fractions.
  • new specification on the sulfur content in transportation fuels normally requires increased hydrotreating in the refineries, a type of processing that consumes hydrogen, thereby contributing to a hydrogen imbalance in the refineries.
  • Upgrading of the heavier fractions can be done either by “carbon-rejection” type of processes such as delayed coking or catalytic cracking, or by hydrogen addition such as hydrocracking.
  • the former produces “coke” which is burnt as energy input in the processing/upgrading or sold as a product (petroleum coke), while the latter gives a higher yield of high-value liquid products of the kind mentioned above, at the penalty of higher hydrogen consumption.
  • the particular high content of residue in heavy oils requires particular refinery configurations to process these crudes, and the high content of metals and carbon residue/asphaltenes in the residue limits the use of catalytic processes available to upgrade the heavy ends of those heavy crudes.
  • the hydrocracking option allows for production of ultra-clean (low sulfur) transportation fuels of a quality in compliance with the most stringent fuel specifications both in EU and in the US. This will normally require a two-step hydrocracking scheme, where the products from the residue hydrocracker must be hydrocracked in a VGO type of hydrocracker to give the ultra-clean transportation fuels.
  • the metals In catalytic hydrocracking of residue, the metals will end up on the catalyst, which by proper treatment can be dissolved and the metals, mainly Vanadium and Nickel, recuperated.
  • the sulfur ends up as H2S which is easily captured and for example converted to elementary sulfur by use of techniques commonly used in refineries today.
  • impurities such as metals and sulfur in the heavy oil, will be properly handed in the upgrader.
  • Heavy oils are, due to their physical properties and particularly the high viscosity, difficult to produce and transport. Technologies have been developed for partial upgrading at the wellhead to make the oil transportable, as an alternative to dilution of the viscous oil by lighter fractions such as typically naphtha.
  • the common solution for the Orinoco bitumen produced in Venezuela is transport by pipeline by naphtha dilution to an upgrader located at the coast, where the naphtha is separated from and recycled, while the crude is partially upgraded to an essentially residue-free synthetic crude with densities in the range of typically 20-32API.
  • the synthetic crude is then exported to a conventional refinery for upgrading to finished products.
  • the amount of hydrogen required depends on the characteristics of the heavy oil, the upgrader/refinery scheme and the types of products, but a simple mass balance demonstrates that production of finished products from an extra-heavy oil requires so much hydrogen that it could possibly serve as a single solution for remote or stranded gas which then must be transported to (or close to) the heavy oil production site. In some cases, the natural gas could even be available as associated gas, produced with the oil.
  • WO03/018958 relates to a combined facility for production of gases for injection into an oil field and production of synthesis gas for synthesis of methanol or other oxygenated hydrocarbons or higher hydrocarbons in a synthesis loop.
  • Synthesis gas comprising a mixture of H 2 and CO is produced from hydrocarbons, preferably from natural gas.
  • the natural gas may be found in the same formations as the heavy oil or in nearby the heavy oil reservoir.
  • Heat from the synthesis gas production is used to produce steam for injection into the formation to lower the viscosity of the heavy oil by heating it.
  • the synthesis gas is used to produce hydrocarbons by use of a Fischer-Tropsch catalyst. At least a part of the produced hydrocarbons is used to dilute the produced heavy hydrocarbons to lower the viscosity to facilitate the transportation of the oil in pipelines.
  • U.S. Pat. No. 4,706,751 describes another heavy oil recovery process for the recovery of heavy oils from deep reservoirs.
  • Reactant streams are produced in a surface process unit.
  • the reactant streams that may be e.g. H 2 and O 2 plus water, or CO and steam plus water, is introduced into the well and reacted in a catalytic reactor downhole to produce high quality steam, H 2 , CO 2 and any gas or vapour that are readily soluble in the heavy oil such as methane, methanol, light hydrocarbons etc.
  • the reactions in the downhole reactor are exothermal and produce heat for steam formation and heating.
  • Cleaning waste gas from the combustion on the production installation can provide CO 2 for injection into oil reservoirs.
  • CO 2 cleaned from the flue gas from gas power plants be reinjected by laying a pipeline from a gas power plant to the production installation for hydrocarbons.
  • the present invention aims at combining various elements of known methods of natural gas conversion and heavy oil upgrading by upgrading of the heavy/extra heavy oil to high value, finished products by the use of large amounts of hydrogen generated from the natural gas.
  • byproducts we obtain steam, CO 2 , water and optionally N 2 , which can be used for enhanced recovery of the heavy oils from the reservoir.
  • the capture of CO 2 from the hydrogen generation plant represents a significant potential of reduction of the CO 2 emissions from the upgrading by injection of the CO 2 into underground storage (sequestering), or injection into to reservoir to obtain enhanced oil recovery.
  • an integrated process for production and upgrading of heavy and extra-heavy crude oil comprising (a) reforming of natural gas to produce hydrogen, CO 2 and steam (b) separating the produced hydrogen from the CO 2 , steam and any other gases to give a hydrogen rich fraction and a CO 2 rich fraction and steam, (c) injecting the steam alone or in combination with the CO 2 rich fraction into the reservoir containing heavy or extra heavy oil to increase the oil recovery, and (d) upgrading/refining of the heavy or extra heavy oil by hydroprocessing, comprising hydrocracking and hydrotreating using the hydrogen rich fraction in the hydroprocessing steps.
  • hydrotreating comprises, as used in the present invention, removal of sulfur, nitrogen and metals as well as hydrogenation of olefins and aromatics.
  • step (a) is steam reforming.
  • the steam reforming may be performed under supercritical conditions.
  • the reforming in step (a) is autothermal reforming or partial oxidation.
  • Air may be used as oxidizer in the autothermal reformer or in the partial oxidation reactor.
  • the process comprises the additional step of air separation to produce purified oxygen comprising more than 95%, preferably more than 98% oxygen, that is used as oxidizer in the reforming.
  • purified oxygen comprising more than 95%, preferably more than 98% oxygen, that is used as oxidizer in the reforming.
  • the use of purified oxygen in the reforming and separation of the reformed gases reduces the gas volume in the reactors and the separation units. Accordingly the volume and building costs may be reduced and the separation of hydrogen from the remaining gases is more effective.
  • purified nitrogen co-produced with the purified oxygen is injected into the reservoir together with the CO 2 rich fraction in step (c) to stimulate the oil production.
  • Nitrogen is effective as pressure support in the reservoir together with the CO 2 rich fraction. It is therefore cost effective to use the produced purified nitrogen for injection.
  • the reformed gas from steam reforming, partial combustion or autothermal reforming comprises CO.
  • the CO is therefore preferably converted by a water gas shift reaction to produce additional CO 2 and H 2 .
  • the heavy or extra heavy oil is partially upgraded in the reservoir by hydrogen injection.
  • the heavy or extra heavy oil is partially upgraded in a downhole upgrading unit.
  • Partial upgrading of the heavy or extra heavy oil in the reservoir makes the oil less viscous. Upgrading in the reservoir may therefore increase the oil production, whereas both upgrading in the reservoir and in a downhole unit will improve the transportability of the oil
  • the heavy or extra heavy oil is upgraded on an offshore or onshore upgrading facility.
  • At least a part of the heat to increase recovery of the heavy or extra heavy oil is generated by in-situ combustion.
  • geothermal heat is used to increase recovery and transport of the heavy or extra heavy oil.
  • FIG. 1 is a flowchart illustrating a first preferred embodiment
  • FIG. 2 is a flowchart illustrating a second preferred embodiment.
  • Natural gas 115 ton per hour, is introduced into a steam reforming unit 2 via a gas line 1 .
  • Steam reforming is an endothermal reaction.
  • the steam reforming unit comprises a conventional steam generation unit where water is heated and converted into hot steam by combustion of any suitable fuel such as natural gas, lower or higher hydrocarbons.
  • the product gas from the steam reformer is then sent to a shift converter (one or two step) in which CO is converted to CO 2 by the water gas shift reaction, and hydrogen is then separated by means of well known separation techniques, such as membrane separation or separation by absorption based on the different chemical properties of gases e.g. as described in WO00/18681, into a hydrogen rich fraction leaving the steam reformation unit 2 through a hydrogen line 3 and a fraction comprising mainly CO 2 and steam leaving the unit through line 4 .
  • the hydrogen rich fraction in line 3 constitutes about 35 ton per hour, whereas about 300 ton CO 2 per hour and 210 ton steam per hour leaves the unit through line 4 . This concept represents a favourable way of CO 2 capture due to the high concentration of the CO 2 in the process stream.
  • the preparation of a H 2 rich gas and a CO 2 rich gas may be performed high pressure at supercritical conditions as described in WO/00/18681.
  • the CO 2 and steam is led to a unit for heavy oil production 5 and injected to enhance the recovery of heavy oil.
  • Heavy oil produced in the unit for heavy oil production 5 is led from the unit to a unit for heavy oil upgrading 7 through a heavy oil line 6 .
  • the heavy oil is upgraded by several steps of catalytic hydroprocessing of the heavy or extra heavy oil using hydrogen from line 3 , by hydrocracking in combination with hydrotreating steps, to produce valuable liquid products (distillates) from the distillation residue, to saturate unsaturated hydrocarbons and to remove asphaltenes, metals, nitrogen and sulphur from the finished products.
  • the products from the heavy oil upgrading unit 7 leaves the unit through a plurality of lines 8 .
  • Table 1 indicates a typical yield structure from the unit 7 .
  • TABLE 1 Product Ton per hour C-range Naphtha 200 C5-C8 Kerosine 140 C8-C12 Diesel 580 C12-C22 VGO 300 C22-380C Fuel oil, sulphur 60 380 C+
  • FIG. 2 illustrates a second preferred embodiment of the present invention, where hydrogen for the heavy oil upgrading and gas for injection into the reservoir is generated by autothermal reforming (ATR) of natural gas.
  • ATR autothermal reforming
  • Natural gas 135 ton per hour (221.000 Sm 3 per hour), is introduced through a gas line 10 and O 2 (from an air separation unit) is introduced through a line 10 ′ into an ATR unit 11 .
  • the ATR unit 11 comprises one or more autothermal reforming reactors wherein natural gas is reformed by steam reforming combined with partial combustion. Steam reforming is, as mentioned above, an endothermal reaction and the energy required is supplied from partial combustion of a part of the natural gas in the same reactor according to the following reactions: Steam reforming CH 4 +H 2 O ⁇ CO+3H 2 Partial combustion CH 4 + 3/2O 2 ⁇ CO+2H 2 O
  • the CO is thereafter converted into CO 2 according the following reaction: Water gas shift CO+H 2 O ⁇ CO 2 +H 2
  • Hydrogen, 35 ton per hour, is separated from the remaining gases as described in example 1 and a hydrogen rich fraction is led into a hydrogen line 12 to a heavy oil upgrading unit 17 .
  • Oxygen for the partial combustion is preferably introduced into the reactor(s) as purified oxygen or oxygen enriched air.
  • Purified oxygen is preferred as the absence of the inert nitrogen in the reactor reduces the total gas in the system and simplifies the separation of hydrogen.
  • the purified oxygen is generated in an air separation unit (ASU), separating oxygen and nitrogen in two fractions.
  • ASU air separation unit
  • the nitrogen, 4.1 GSm3/y, from the ASU is led through a nitrogen line 13 and CO 2 , 350 ton per hour from the ATR unit 11 is led through a line 14 to a unit for heavy oil production 15 .
  • the steam amount available for injection is the difference between the steam produced in the synthesis gas heat recovery section and the steam needed for production of 70 MW power for the ASU.
  • the nitrogen, CO 2 and steam are injected to enhance the recovery of heavy oil.
  • Heavy oil produced in the unit for heavy oil production 15 is led from the unit to a unit for heavy oil upgrading 17 through a heavy oil line 16 .
  • the products from the unit for heavy oil upgrading correspond to the products described in Example 1.
  • the air separation unit can deliver 23040 MTPD N 2 and 3840 MTPD 02.
  • This air separation unit requires approximately 70 MW of power, which is delivered in the form of high-pressure steam from the synthesis gas section.
  • the ratio between O2 and natural gas will be about 0.65 giving a nitrogen production of about 4.1 GSm3/year (2.34*1.75 GSm3/year)
  • the nitrogen is extracted at 3 bar and 0 degrees C.
  • the gas is compressed to 220 bars for injection (IOR). Compression requires approximately 180 MW.
  • the oxygen is fed to an ATR for production of synthesis gas from natural gas.
  • the process operates with a steam/carbon ratio of 0.6.
  • the temperature and pressure at the outlet from the ATR is 1030 degrees Celsius and 45 bars respectively. See Table 2 for the natural gas composition. Note! All compositions are given on a dry basis, i.e. without water. TABLE 2 Composition of feeds to synthesis gas section Natural gas Oxygen Mole % Mole % CH 4 83.7 C 2 H 6 5.2 C 3+ 3.2 CO 2 5.2 N 2 + Ar 2.7 1.0 O 2 0.0 99.0 H 2 O 0.0 Sum 100 Total [Sm 3 /hr] 221 000 190 850
  • the synthesis gas is further sent to CO shift conversion.
  • the gas mixture into the shift reactor can have a varying composition depending on the conditions in the ATR (steam ratio, pressure and temperature).
  • One-step shift reactor may convert the CO down to a few percent.
  • a two-step shift converter may decrease the CO content in the gas far below 1 percent.
  • the gas mixture out from the shift reactor contains significant amounts of steam. After cooling to e.g. 40° C. most of the steam will be condensed out.
  • the separation of CO 2 may be performed by amine washing (e.g. ethanol amine) capturing above 90% of the CO 2 in the gas.
  • amine washing e.g. ethanol amine
  • the CO 2 rich amine solution is fed to a stripping unit where the CO 2 will be liberated because of the temperature increase and pressure reduction, further CO 2 can be set free from the amine solution by stripping with steam.
  • the remaining gas is used in fired heaters for superheating of steam in power production and preheating of natural gas feeds.
  • the unit for heavy oil upgrading/refining may in both examples one can envisage use the gases produced in the present concept for both downhole upgrading and enhanced oil recovery.
  • Hydrogen could be used for partial downhole upgrading to obtain a transportable oil which would be upgraded to finished products at a nearby upgrader or exported to another refinery.
  • a downhole unit will reduce the loss of energy (heat) in transport lines of steam, gases and oil. Additionally, dilution of the heavy oil to make it flow through transport lines will be unnecessary.
  • the energy needed to increase the transportability of the heavy oil in the reservoir may also be geo heat or a combination of geo heat and energy produced in the reforming process both down hole and in more conventional facilities off- or onshore.
  • Any hydrogen produced in the gas conversion part i.e. ATR or steam reforming units, can be used for other purposes, such as fuel for fuel cells, and for other industrial purposes such as production of ammonia, methanol and synthetic fuel.

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WO2005007776A1 (fr) 2005-01-27

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