Classifications

• • 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
• • 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
• • 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
  • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/002—Removal of contaminants
  • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
  • C10K1/005—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/08—Production of synthetic natural gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/101—Removal of contaminants
• • 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
• • 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
  • F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
  • F25J3/04533—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the direct combustion of fuels in a power plant, so-called "oxyfuel combustion"
• • 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
  • F25J3/04527—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
• • 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
  • F25J3/04527—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
  • F25J3/04545—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 for the gasification of solid or heavy liquid fuels, e.g. integrated gasification combined cycle [IGCC]
• • 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
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  • 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
  • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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  • 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
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  • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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  • 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
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  • C01B2203/0415—Purification by absorption in liquids
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  • C01B2203/0435—Catalytic purification
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  • C01B2203/0465—Composition of the impurity
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  • C01B2203/08—Methods of heating or cooling
  • C01B2203/0872—Methods of cooling
  • C01B2203/0888—Methods of cooling by evaporation of a fluid
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  • C01B2203/14—Details of the flowsheet
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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
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• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
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  • C10J2300/0913—Carbonaceous raw material
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• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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  • F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E20/00—Combustion technologies with mitigation potential
  • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
  • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
  • Y02P20/145—Feedstock the feedstock being materials of biological origin
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

• the present invention relates to an enhanced oil recovery process that is integrated with a synthesis gas generation process, such as gasification or reforming, and an air separation process for generating (i) an oxygen stream for use, for example, in the syngas process or a combustion process, and (ii) a nitrogen stream for EOR use.
• a synthesis gas generation process such as gasification or reforming
• an air separation process for generating (i) an oxygen stream for use, for example, in the syngas process or a combustion process, and (ii) a nitrogen stream for EOR use.
• oil is produced using the natural pressure of an oil reservoir to drive the crude into the well bore from where it is brought to the surface with conventional pumps. After some period of production, the natural pressure of the oil reservoir decreases and production dwindles.
• producers incorporated secondary recovery by utilizing injected water, steam and/or natural gas to drive the crude to the well bore prior to pumping it to the surface.
• EOR enhanced oil recovery
• EOR based on high pressure nitrogen injection can also involve other techniques such as C0 2 injection/flood, which may be done concurrently and/or consecutively with the nitrogen injection.
• CO 2 injection also helps to repressurize the oil reservoir.
• the high-pressure CO 2 also acts as a solvent, dissolving the residual oil, thereby reducing its viscosity and improving its flow characteristics, allowing it to be pumped out of an aging reservoir.
• Nitrogen is generally available from air separation processes, but it is not considered economical to utilize air separation processes solely for the generation of nitrogen for EOR.
• CO 2 from natural sources can be utilized, but generally requires the natural source to be in the proximity of the oil reservoir to avoid the construction and use of pipelines, which could make such use uneconomical.
• Use of CO 2 from combustion sources has also been considered (see, for example, US7299868 and publications cited therein), but the separation of CO 2 from the combustion gases is difficult and generally not considered economical.
• Synthesis gas production operations include, for example, catalytic gasification and hydromethanation processes, non-catalytic gasification processes and methane reforming processes. These processes typically produce one or more of methane, hydrogen and/or syngas (a mixture of hydrogen and carbon monoxide) as a raw gas product, which can be processed and ultimately used for power generation and/or other industrial applications. These processes also produce CO 2 , which is removed via acid gas removal processes, as is generally known to those of ordinary skill in the relevant art. Historically, this CO 2 has simply been vented to the atmosphere but, in view of environmental concerns, capture and sequestration/use of this CO 2 is becoming a necessity. EOR is thus a logical outlet for CO 2 streams from synthesis gas production operations.
• At least one such synthesis gas production operation which utilizes a CO 2 by-product stream for EOR currently exists at the Great Plains Synfuels Plant (near Beulah, North Dakota USA).
• coal/lignite is gasified to a synthesis gas stream containing carbon dioxide, which is separated via a solvent-based acid gas removal technique.
• the resulting CO 2 stream (which is greater than 95% pure) is compressed and transported via a 205-mile supercritical CO 2 pipeline to oil fields in Canada for use in EOR operations.
• This operation is described in more detail in Perry and Eliason, "CO 2 Recovery and Sequestration at Dakota Gasification Company" (October 2004) (available from www.gasification.org), and on the Dakota Gasification Company website (www.dakotagas.com).
• a disadvantage in this operation is the pipeline, as supercritical CO 2 is considered a hazardous material.
• the construction, permitting, operation and maintenance of a supercritical CO 2 pipeline, particularly one as long as 205 miles, is expensive.
• a more advantageous way to get the C0 2 from the synthesis gas operation to the EOR site would, therefore, be highly desirable.
• the present invention provides an integrated process to (i) produce an acid gas-depleted product gas stream, (ii) produce an oxygen-rich gas stream, (iii) produce a hydrocarbon-containing fluid from an underground hydrocarbon reservoir via a hydrocarbon production well, and (iv) enhance production of the hydrocarbon-containing fluid from the underground hydrocarbon reservoir, the process comprising the steps of:
• synthesis gas stream from a carbonaceous feedstock, the synthesis gas stream comprising (a) carbon dioxide, and (b) at least one of hydrogen and methane;
• the present invention provides a process to enhance production of a hydrocarbon-containing fluid from an underground hydrocarbon reservoir via a hydrocarbon production well, by injecting a pressurized nitrogen stream into the underground hydrocarbon reservoir, wherein the pressurized nitrogen stream is generated by a process comprising the steps of:
• (V) optionally treating the gaseous hydrocarbon product stream in the acid gas removal unit to produce an acid-gas depleted gaseous hydrocarbon product stream;
• the carbon dioxide-rich stream generated from acid gas removal is pressurized to generate a pressurized carbon dioxide stream, at least a portion of which is injected into the underground hydrocarbon reservoir.
• steps (7) and (VI) are present, and the combustion is used to produce energy (for example, mechanical and/or electrical energy) that is used at least in part for the air separation step (steps (8) and (VII)) and/or pressurization (compression) steps (steps (9) and (VIII), and/or CO 2 compression).
• energy for example, mechanical and/or electrical energy
• the invention provides an apparatus for producing a hydrocarbon- containing fluid, an acid gas-depleted product gas stream and an oxygen-rich stream, the apparatus comprising:
• an air separation unit adapted to (i) receive an air stream and (ii) separate the air stream into an oxygen-rich stream and a nitrogen-rich recycle stream;
• the injection well is further adapted to inject a pressurized carbon dioxide stream into the underground hydrocarbon reservoir
• the apparatus further comprises a compressor unit in fluid communication with the acid gas removal unit and the injection well, the compressor unit adapted to (i) receive the carbon dioxide-rich stream, and (ii) compress the carbon dioxide recycle stream to generate the pressurized carbon dioxide stream, and (iii) provide the pressurized carbon dioxide stream to the injection well.
• the acid gas removal unit is adapted to receive a combined stream of the synthesis gas and the gaseous hydrocarbon product stream, and treat the combined stream to remove acid gases and produce an acid gas- depleted product gas stream and a carbon dioxide-rich stream.
• the acid gas removal unit is also adapted to receive the gaseous hydrocarbon product stream from the separation device, and treat the gaseous hydrocarbon product stream to remove acid gases and produce an acid gas- depleted gaseous hydrocarbon product stream.
• the acid gas-depleted product gas stream will comprise both the acid gas-depleted gaseous hydrocarbon product stream and an acid gas-depleted synthesis gas stream (separate or combined).
• Figure 1 is a diagram of an embodiment of an integrated process in accordance with the present invention.
• Figure 2 is a diagram of a first specific embodiment of the integrated process in accordance with the present invention.
• Figure 3 is a diagram of an embodiment of the gas processing portion of the integrated process of Figure 2.
• Figure 4 is a diagram of a second specific embodiment of the integrated process in accordance with the present invention.
• Figure 5 is a diagram of an embodiment of the gas processing portion of the integrated process of Figure 4.
• Figure 6 is a diagram of an electrical power block suitable for use in conjunction with the present invention. Detailed Description
• the present disclosure relates to integrating synthesis gas production processes and air separation processes with enhanced oil recovery processes. Further details are provided below.
• pressures expressed in psi units are gauge, and pressures expressed in kPa units are absolute.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.
• "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• substantially portion means that greater than about 90% of the referenced material, preferably greater than about 95% of the referenced material, and more preferably greater than about 97% of the referenced material.
• the percent is on a molar basis when reference is made to a molecule (such as methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as the liquid component of the hydrocarbon-containing fluid).
• the term "predominant portion”, as used herein, unless otherwise defined herein, means that greater than about 50% of the referenced material. The percent is on a molar basis when reference is made to a molecule (such as hydrogen, methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as the liquid component of the hydrocarbon-containing fluid).
• hydrocarbon-containing fluid means a fluid comprising any hydrocarbon liquid and/or gas.
• a hydrocarbon-containing fluid may also comprise solid particles. Oil, gas-condensate and the like, and also their mixtures with other liquids such as water, may be examples of a liquid contained in a hydrocarbon-containing fluid. Any gaseous hydrocarbon (for example, methane, ethane, propane, propylene, butane or the like), and mixtures of gaseous hydrocarbons, may be contained in a hydrocarbon-containing fluid.
• the hydrocarbon-containing fluid is recovered from an underground hydrocarbon reservoir, such as an oil-bearing formation, a gas-condensate reservoir, a natural gas reservoir and the like.
• carbonaceous as used herein is synonymous with hydrocarbon.
• carbonaceous material as used herein is a material containing organic hydrocarbon content. Carbonaceous materials can be classified as biomass or non-biomass materials as defined herein.
• biomass refers to carbonaceous materials derived from recently (for example, within the past 100 years) living organisms, including plant-based biomass and animal-based biomass.
• biomass does not include fossil-based carbonaceous materials, such as coal. For example, see US2009/0217575A1 and US2009/0217587A1.
• plant-based biomass means materials derived from green plants, crops, algae, and trees, such as, but not limited to, sweet sorghum, bagasse, sugarcane, bamboo, hybrid poplar, hybrid willow, albizia trees, eucalyptus, alfalfa, clover, oil palm, switchgrass, sudangrass, millet, jatropha, and miscanthus (e.g., Miscanthus x giganteus).
• Biomass further include wastes from agricultural cultivation, processing, and/or degradation such as corn cobs and husks, corn stover, straw, nut shells, vegetable oils, canola oil, rapeseed oil, biodiesels, tree bark, wood chips, sawdust, and yard wastes.
• biomass means wastes generated from animal cultivation and/or utilization.
• biomass includes, but is not limited to, wastes from livestock cultivation and processing such as animal manure, guano, poultry litter, animal fats, and municipal solid wastes (e.g., sewage).
• non-biomass means those carbonaceous materials which are not encompassed by the term “biomass” as defined herein.
• non-biomass include, but is not limited to, anthracite, bituminous coal, sub-bituminous coal, lignite, petroleum coke, asphaltenes, liquid petroleum residues or mixtures thereof.
• anthracite bituminous coal
• sub-bituminous coal lignite
• petroleum coke lignite
• asphaltenes liquid petroleum residues or mixtures thereof.
• petroleum coke and “petcoke” as used here include both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues - "resid petcoke”); and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands - “tar sands petcoke”).
• Such carbonization products include, for example, green, calcined, needle and fluidized bed petcoke.
• Resid petcoke can also be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil, which petcoke contains ash as a minor component, typically about 1.0 wt% or less, and more typically about 0.5 wt% of less, based on the weight of the coke.
• the ash in such lower-ash cokes comprises metals such as nickel and vanadium.
• Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand.
• Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the tar sands petcoke.
• the ash in such higher-ash cokes comprises materials such as silica and/or alumina.
• Petroleum coke has an inherently low moisture content, typically, in the range of from about 0.2 to about 2 wt% (based on total petroleum coke weight); it also typically has a very low water soaking capacity to allow for conventional catalyst impregnation methods.
• the resulting particulate compositions contain, for example, a lower average moisture content which increases the efficiency of downstream drying operation versus conventional drying operations.
• the petroleum coke can comprise at least about 70 wt% carbon, at least about 80 wt% carbon, or at least about 90 wt% carbon, based on the total weight of the petroleum coke.
• the petroleum coke comprises less than about 20 wt% inorganic compounds, based on the weight of the petroleum coke.
• asphalte as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, for example, from the processing of crude oil and crude oil tar sands.
• coal as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof.
• the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight.
• the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on the total coal weight.
• Examples of useful coal include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (NO), Utah Blind Canyon, and Powder River Basin (PRB) coals.
• Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt%, from about 5 to about 7 wt%, from about 4 to about 8 wt%, and from about 9 to about 1 1 wt%, ash by total weight of the coal on a dry basis, respectively.
• the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, for example, "Coal Data: A Reference", Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
• the ash produced from combustion of a coal typically comprises both a fly ash and a bottom ash, as are familiar to those skilled in the art.
• the fly ash from a bituminous coal can comprise from about 20 to about 60 wt% silica and from about 5 to about 35 wt% alumina, based on the total weight of the fly ash.
• the fly ash from a sub-bituminous coal can comprise from about 40 to about 60 wt% silica and from about 20 to about 30 wt% alumina, based on the total weight of the fly ash.
• the fly ash from a lignite coal can comprise from about 15 to about 45 wt% silica and from about 20 to about 25 wt% alumina, based on the total weight of the fly ash. See, for example, Meyers, et al. "Fly Ash. A Highway Construction Material," Federal Highway Administration, Report No. FHWA-IP-76-16, Washington, DC, 1976.
• the bottom ash from a bituminous coal can comprise from about 40 to about 60 wt% silica and from about 20 to about 30 wt% alumina, based on the total weight of the bottom ash.
• the bottom ash from a sub-bituminous coal can comprise from about 40 to about 50 wt% silica and from about 15 to about 25 wt% alumina, based on the total weight of the bottom ash.
• the bottom ash from a lignite coal can comprise from about 30 to about 80 wt% silica and from about 10 to about 20 wt% alumina, based on the total weight of the bottom ash. See, for example, Moulton, Lyle K. "Bottom Ash and Boiler Slag," Proceedings of the Third International Ash Utilization Symposium, U.S. Bureau of Mines, Information Circular No. 8640, Washington, DC, 1973.
• a carbonaceous material such as methane can be biomass or non-biomass under the above definitions depending on its source of origin.
• unit refers to a unit operation. When more than one "unit” is described as being present, those units are operated in a parallel fashion.
• an acid gas removal unit may comprise a hydrogen sulfide removal unit followed in series by a carbon dioxide removal unit.
• a contaminant removal unit may comprise a first removal unit for a first contaminant followed in series by a second removal unit for a second contaminant.
• a compressor may comprise a first compressor to compress a stream to a first pressure, followed in series by a second compressor to further compress the stream to a second (higher) pressure.
• an acid gas-depleted product gas steam (38), an oxygen-rich stream (14) and a hydrocarbon-containing fluid (82) are produced in an integrated EOR, air separation and synthesis gas production process as illustrated in Figures 1-6.
• the synthesis gas production system (facility) and air separation units are both proximate to the EOR location (field), such as on the same or an adjoining land parcel.
• the EOR portion of the process involves injecting a pressurized nitrogen stream (19), and optionally a pressurized carbon dioxide stream (89), via an injection well (500) (one or more) into an underground hydrocarbon reservoir (20) utilizing techniques well known to those of ordinary skill in the relevant art.
• the pressurized nitrogen stream (19) assists in the repressurization of the underground reservoir.
• the pressurized nitrogen stream (19) will be injected into the underground reservoir at a pressure of at least about 1200 psig (about 8375 kPa), or at least about 1500 psig (about 10444 kPa), or at least about 2000 psig (about 13891 kPa).
• the pressurized carbon dioxide stream (89) which will typically be in a supercritical fluid state, serves to enhance production of a hydrocarbon fluid (82) from a production well (600) through a combination of mechanisms typically involving a repressurization of the underground reservoir and a viscosity reduction of the trapped hydrocarbon (improving flow properties).
• the pressurized carbon dioxide stream (89) will also be injected into the underground reservoir at a pressure of at least about 1200 psig (about 8375 kPa), or at least about 1500 psig (about 10444 kPa), or at least about 2000 psig (about 13891 kPa).
• EOR using carbon dioxide and nitrogen can utilize co-injection (both at the same time in the same location), concurrent injection (both at the same time at different locations), consecutive injection (one followed by the other in the same or separate locations) or some combination of these various techniques.
• EOR can also involve co- injection, concurrent injection or consecutive injection of pressurized water, steam and other fluids.
• the actual carbon dioxide/nitrogen-based EOR process utilized is not critical to the present invention in its broadest sense.
• the resulting hydrocarbon-containing fluid (82) is produced and recovered through a hydrocarbon production well (600) (one or more).
• the produced hydrocarbon-containing fluid (82) will typically contain liquid and gas hydrocarbon components, as well as other liquid and gaseous components depending on the hydrocarbon reservoir and EOR conditions.
• the liquid hydrocarbon component can generally be considered as a crude oil, while the gaseous hydrocarbon component will typically comprise hydrocarbons that are gases at ambient conditions, such as methane, ethane, propane, propylene and butane (typical components of natural gas). Other typical liquid components include water or brine.
• the hydrocarbon-containing fluid (82) may also comprise carbon dioxide, and may comprise other gaseous components such as hydrogen sulfide (from a sour well) and nitrogen.
• the hydrocarbon-containing fluid (82) may also include solid carbon and mineral matter.
• the produced hydrocarbon-containing fluid (82) is passed to a separation device (300) to separate the gaseous components from the liquid/solid components to generate a gaseous hydrocarbon product stream (84), a liquid hydrocarbon product stream (85) and, optionally, a stream (86) containing solids components from the hydrocarbon-containing fluid (82).
• the solids may also optionally be carried with the liquid hydrocarbon product stream (85) for later separation, or separated out prior to separation device (300), by well- known techniques such as settling, centrifugation and/or filtration.
• larger/denser solids are separated in conjunction with separation device (300), and finer solids that may become entrained in liquid hydrocarbon product stream (85) are separated subsequently through well-known techniques such as filtration.
• Suitable separation devices for use as separation device (300) are well known to those of ordinary skill in the art and include, for example, single and multistage horizontal separators and cyclones.
• the actual separation device utilized is not critical to the present invention in its broadest sense.
• the liquid hydrocarbon product stream (85) can subsequently be processed to separate out the water and other contaminants, then further processed (e.g., refined) to a variety of end products or for a variety of end uses, as is well-known to those or ordinary skill in the relevant art.
• a stream (86) containing solids components that will typically be removed from separation device (300) as a concentrated slurry or with some portion of the liquid content of the hydrocarbon-containing fluid (82). Oil that may be withdrawn with the solids in stream (86) can be recovered from the solids via washing or other techniques well- known to those of ordinary skill in the relevant art.
• the resulting gaseous hydrocarbon product stream (84) exiting separation device (300) typically comprises at least a substantial portion (or substantially all) of the gaseous components from the hydrocarbon-containing fluid (82), including at least a substantial portion (or substantially all) of the gaseous hydrocarbons (and carbon dioxide to the extent present) from the hydrocarbon-containing fluid (82).
• the gaseous hydrocarbon product stream (84) may also comprise minor amounts of water vapor (which should be substantially removed prior to further treatment, for example, in acid gas removal unit (200) as discussed below) as well as other contaminants if present, such as hydrogen sulfide.
• the resulting gaseous hydrocarbon stream (84) will contain a substantial portion (or substantially all) of the acid gases, and in one embodiment will be subject to acid gas removal to remove and recover the acid gases.
• gaseous hydrocarbon product stream (84) exiting separation device (300) may be combined with a synthesis gas stream (50), or otherwise co-processed with synthesis gas stream (50) in an acid gas removal unit (200) as discussed below.
• gaseous hydrocarbon product stream (84) Prior to combination with synthesis gas stream (50) or co-processing in acid gas removal unit (200), gaseous hydrocarbon product stream (84) may optionally be compressed or heated (not depicted) to temperature and pressure conditions suitable for combination or other downstream processing as further described below.
• All or a portion of the gaseous hydrocarbon product stream (84) may, in addition or alternatively, be combusted in a power block (760a), for example, for electrical power (79a) and/or steam generation.
• An oxygen-rich gas stream (14c) that comprises at least a portion of oxygen-rich stream (14) from air separation unit (800) may be utilized in power block (760a) as discussed below.
• Synthesis gas stream (50) contains (i) carbon dioxide, and (ii) at least one of hydrogen and methane.
• the actual composition of synthesis gas stream (50) will depend on the synthesis gas process and carbonaceous feedstock utilized to generate the stream, including any gas processing that may occur before acid gas removal unit (200) or optional combination with gaseous hydrocarbon stream (84).
• synthesis gas stream (50) comprises carbon dioxide and hydrogen. In another embodiment, synthesis gas stream (50) comprises carbon dioxide and methane. In another embodiment, synthesis gas stream (50) comprises carbon dioxide, methane and hydrogen.
• the synthesis gas stream (50) may also contain other gaseous components such as, for example, carbon monoxide, hydrogen sulfide, steam and other gaseous hydrocarbons again depending on the synthesis gas production process and carbonaceous feedstock.
• Synthesis gas stream (50) is generated in a synthesis gas production system (100). Any synthesis gas generating process can be utilized in the context of the present invention, so long as the synthesis gas generating process (including gas processing prior to optional combination with gaseous hydrocarbon stream (84) or prior to acid gas removal unit (200)) results in a synthesis gas stream as required in the context of the present invention. Suitable synthesis gas processes are generally known to those of ordinary skill in the relevant art, and many applicable technologies are commercially available.
• An oxygen-rich gas stream (14a) that comprises at least a portion of oxygen-rich stream (14) from air separation unit (800) may optionally be utilized in the synthesis gas production system (100) as described below.
• Non-limiting examples of different types of suitable synthesis gas generation processes are discussed below. These may be used individually or in combination. All synthesis gas generation process will involve a reactor, which is generically depicted as (110) in Figures 3 and 5, where a carbonaceous feedstock (10) will be processed to produce synthesis gases, which may be further treated prior to optional combination with gaseous hydrocarbon stream (84) and/or prior to acid gas removal unit (200). General reference can be made to Figures 3 and 5 in the context of the various synthesis gas generating processes described below.
• the synthesis gas generating process is based on a gas-fed methane partial oxidation/reforming process, such as non-catalytic gaseous partial oxidation, catalytic authothermal reforming or catalytic stream- methane reforming process.
• a gas-fed methane partial oxidation/reforming process such as non-catalytic gaseous partial oxidation, catalytic authothermal reforming or catalytic stream- methane reforming process.
• the methane-containing stream useful in these processes comprises methane in a predominant amount, and may comprise other gaseous hydrocarbon and components.
• Examples of commonly used methane-containing streams include natural gas and synthetic natural gas.
• an oxygen- rich gas stream (14a) is fed into the reactor (110) along with carbonaceous feedstock (10).
• steam (16) may also be fed into the reactor (110).
• steam-methane reforming steam (16) is fed into the reactor along with the carbonaceous feedstock (10).
• minor amounts of other gases such as carbon dioxide, hydrogen and/or nitrogen may also be fed in the reactor (110).
• the synthesis gas generating process is based on a non- catalytic thermal gasification process, such as a partial oxidation gasification process (like an oxygen-blown gasifier), where a non-gaseous (liquid, semi-solid and/or solid) hydrocarbon is utilized as the carbonaceous feedstock (10).
• a non-catalytic thermal gasification process such as a partial oxidation gasification process (like an oxygen-blown gasifier)
• a non-gaseous (liquid, semi-solid and/or solid) hydrocarbon is utilized as the carbonaceous feedstock (10).
• Oxygen-blown solids/liquids gasifiers potentially suitable for use in conjunction with the present invention are, in a general sense, known to those of ordinary skill in the relevant art and include, for example, those based on technologies available from Royal Dutch Shell pic, ConocoPhillips Company, Siemens AG, Lurgi AG (Sasol), General Electric Company and others.
• Other potentially suitable syngas generators are disclosed, for example, in US2009/0018222A1, US2007/0205092A1 and US6863878.
• an oxygen-rich gas stream (14a) is fed into the reactor (110) along with the carbonaceous feedstock (10).
• steam (16) may also be fed into the reactor (110), as well as other gases such as carbon dioxide, hydrogen, methane and/or nitrogen.
• steam (16) may be utilized as an oxidant at elevated temperatures in place of all or a part of the oxygen-rich gas stream (14a).
• the gasification in the reactor (110) will typically occur in a fluidized bed of the carbonaceous feedstock (10) that is fluidized by the flow of the oxygen-rich gas stream (14a), steam (16) and/or other fluidizing gases (like carbon dioxide and/or nitrogen) that may be fed to reactor (110).
• thermal gasification is a non-catalytic process, so no gasification catalyst needs to be added to the carbonaceous feedstock (10) or into the reactor (110); however, a catalyst that promotes syngas formation may be utilized.
• thermal gasification processes are typically operated under high temperature and pressure conditions, and may run under slagging or non-slagging operating conditions depending on the process and carbonaceous feedstock.
• Reaction and other operating conditions, and equipment and configurations, of the various reactors and technologies are in a general sense known to those of ordinary skill in the relevant art, and are not critical to the present invention in its broadest sense.
• the synthesis gas generating process is a catalytic gasification/hydromethanation process, in which gasification of a non-gaseous carbonaceous feedstock (10) takes place in a reactor (110) in the presence of steam and a catalyst to result in a methane-enriched gas stream as the synthesis gas stream (50), which typically comprises methane, hydrogen, carbon monoxide, carbon dioxide and steam.
• the overall reaction is essentially thermally balanced; however, due to process heat losses and other energy requirements (such as required for evaporation of moisture entering the reactor with the feedstock), some heat must be added to maintain the thermal balance.
• the reactions are also essentially syngas (hydrogen and carbon monoxide) balanced (syngas is produced and consumed); therefore, as carbon monoxide and hydrogen are withdrawn with the product gases, carbon monoxide and hydrogen need to be added to the reaction as required to avoid a deficiency.
• the carbonaceous feedstocks useful in these processes include, for example, a wide variety of biomass and non-biomass materials.
• Catalysts utilized in these processes include, for example, alkali metals, alkaline earth metals and transition metals, and compounds, mixtures and complexes thereof.
• the temperature and pressure operating conditions in a catalytic gasification/hydromethanation process are typically milder (lower temperature and pressure) than a non-catalytic gasification process, which can sometimes have advantages in terms of cost and efficiency.
• Catalytic gasification/hydromethanation processes and conditions are disclosed, for example, in US3828474, US3998607, US4057512, US4092125, US4094650, US4204843 US4468231, US4500323, US4541841, US4551155, US4558027, US4606105, US4617027 US4609456, US5017282, US5055181, US6187465, US6790430, US6894183, US6955695 US2003/0167961A1 and US2006/0265953A1, as well as in commonly owned US2007/0000177A1 , US2007/0083072A1 , US2007/0277437A1 , US2009/0048476A1
• All of the above described synthesis gas generation processes typically will generate a synthesis gas stream (50) of a temperature higher than suitable for feeding downstream gas processes (including acid gas removal unit (200)) and/or combining with gaseous hydrocarbon stream (84), so upon exit from reactor (110) the synthesis gas stream (50) is typically passed through a heat exchanger unit (140) to remove heat energy and generate a cooled synthesis gas stream (52).
• the heat energy recovered in heat exchanger unit (140) can be used, for example, to generate steam and/or superheat various process streams, as will be recognized by a person of ordinary skill in the art. Any steam generated can be used, for example, for internal process requirements and/or to generate electrical power.
• the resulting cooled synthesis gas stream (52) will typically exit heat exchanger unit (140) at a temperature ranging from about 450°F (about 232°C) to about 1 100°F (about 593°C), more typically from about 550°F (about 288°C) to about 950°F (about 510°C), and at a pressure suitable for subsequent acid gas removal processing (taking into account any intermediate processing).
• this pressure will be from about 50 psig (about 446 kPa) to about 800 psig (about 5617 kPa), more typically from about 400 psig (about 2860 kPa) to about 600 psig (about 4238 kPa).
• Synthesis gas stream (50) and gaseous hydrocarbon stream (84) may be processed separately, or may optionally be combined at various points and individually or co-processed in various treatment processes, or optionally combined and co-treated at or in acid gas removal unit (200). Specific embodiments where synthesis gas stream (50) and gaseous hydrocarbon stream (84) are combined and/or co-processed are depicted in Figures 2-5. The combination point and processing variations will be primarily dependent on the composition, temperature and pressure of the two streams, and any desired end products.
• Processing options prior to acid gas removal typically include, for example, one or more of sour shift (700) (water gas shift), contaminant removal (710) and dehydration (720). While these intermediate processing steps can occur in any order, dehydration (720) will usually occur just prior to acid gas removal (last in the series), as a substantial portion of any water in synthesis gas stream (50) and gaseous hydrocarbon stream (84) desirably should be removed prior to treatment in acid gas removal unit (200).
• synthesis gas stream (50) and gaseous hydrocarbon stream (84) are combined prior to acid gas removal unit (200) to generate a combined gas stream (60).
• synthesis gas stream (50) and gaseous hydrocarbon stream (84) are combined prior to dehydration (720).
• synthesis gas stream (50) and gaseous hydrocarbon stream (84) are separately dehydrated (720 and 720a) and combined before or during acid gas removal.
• Combination of the two streams may also require compression or expansion of one or both of the streams.
• the gaseous hydrocarbon stream (84) will require at least some compression prior to combination with synthesis gas stream (50).
• synthesis gas stream (50) and gaseous hydrocarbon stream (84) are co-processed within acid gas removal unit (200), as discussed in more detail below.
• a sour shift reactor 700
• the gases undergo a sour shift reaction (also known as a water-gas shift reaction, see formula (II) above) in the presence of an aqueous medium (such as steam) to convert at least a predominant portion (or a substantial portion, or substantially all) of the CO to CO 2 , which also increases the fraction of H 2 in order to produce a hydrogen- enriched stream (54).
• a sour shift reaction also known as a water-gas shift reaction, see formula (II) above
• an aqueous medium such as steam
• a sour shift process is described in detail, for example, in US7074373.
• the process involves adding water, or using water contained in the gas, and reacting the resulting water- gas mixture adiabatically over a steam reforming catalyst.
• Typical steam reforming catalysts include one or more Group VIII metals on a heat-resistant support.
• Methods and reactors for performing the sour gas shift reaction on a CO-containing gas stream are well known to those of skill in the art. Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream.
• the sour gas shift can be performed in a single stage within a temperature range from about 100°C, or from about 150°C, or from about 200°C, to about 250°C, or to about 300°C, or to about 350°C.
• the shift reaction can be catalyzed by any suitable catalyst known to those of skill in the art.
• Such catalysts include, but are not limited to, Fe 2 0 3 -based catalysts, such as Fe 2 0 3 -Cr 2 0 3 catalysts, and other transition metal-based and transition metal oxide-based catalysts.
• the sour gas shift can be performed in multiple stages. In one particular embodiment, the sour gas shift is performed in two stages. This two-stage process uses a high-temperature sequence followed by a low-temperature sequence. The gas temperature for the high- temperature shift reaction ranges from about 350°C to about 1050°C.
• Typical high- temperature catalysts include, but are not limited to, iron oxide optionally combined with lesser amounts of chromium oxide.
• the gas temperature for the low-temperature shift ranges from about 150°C to about 300°C, or from about 200°C to about 250°C.
• Low-temperature shift catalysts include, but are not limited to, copper oxides that may be supported on zinc oxide or alumina. Suitable methods for the sour shift process are described in previously incorporated US2009/0246120A1.
• the sour shift reaction is exothermic, so it is often carried out with a heat exchanger (not depicted) to permit the efficient use of heat energy.
• Shift reactors employing these features are well known to those of skill in the art. Recovered heat energy can be used, for example, to generate steam, superheat various process streams and/or preheat boiler feed water for use in other steam generating operations.
• An example of a suitable shift reactor is illustrated in previously incorporated US7074373, although other designs known to those of skill in the art are also effective.
• sour shift is present and it is desired to retain some carbon monoxide content
• a portion of the stream can be split off to bypass sour shift reactor (700) and be combined with hydrogen-enriched stream (54) at some point prior to acid gas removal unit (200). This is particularly useful when it is desired to recover a separate methane by-product, as the retained carbon monoxide can be subsequently methanated as discussed below.
• the contamination levels of synthesis gas stream (50) will depend on the nature of the carbonaceous feedstock and the synthesis gas generation conditions. For example, petcoke and certain coals can have high sulfur contents, leading to higher sulfur oxide (SOx), I3 ⁇ 4S and/or COS contamination. Certain coals can contain significant levels of mercury which can be volatilized during the synthesis gas generation. Other feedstocks can be high in nitrogen content, leading to ammonia, nitrogen oxides (NOx) and/or cyanides.
• acid gas removal unit (200) Some of these contaminants are typically removed in acid gas removal unit (200), such as I3 ⁇ 4S and COS. Others such as ammonia and mercury, typically require removal prior to acid gas removal unit (200).
• contaminant removal of a particular contaminant should remove at least a substantial portion (or substantially all) of that contaminant from the so-treated cleaned gas stream (56), typically to levels at or lower than the specification limits for the desired acid gas removal unit (200), or the desired end product.
• gaseous hydrocarbon stream (84) and cooled synthesis gas stream (54) can be combined subsequent to contaminant removal unit (700), this is only shown for exemplification, as the two streams may be combined prior to contaminant removal unit (710), or treated separately for contaminant removal as needed and subsequently combined.
• the synthesis gas stream (50) and gaseous hydrocarbon stream (84), individually or in combination, should be treated to reduce residual water content via a dehydration unit (720) (and (720a) if present) to produce a dehydrated stream (58) (and (58a) if dehydration unit (720a) is present).
• Suitable dehydration units include a knock-out drum or similar water separation device, and/or water absorption processes such as glycol treatment.
• At least the synthesis gas stream (50) (or a derivative stream resulting from intermediate treatment) is processed in an acid gas removal unit (200) to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present), and generate a carbon dioxide-rich stream (87) and an acid gas-depleted synthesis gas stream as the acid gas-depleted product gas stream (38).
• an acid gas removal unit 200 to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present)
• carbon dioxide-rich stream (87) and an acid gas-depleted synthesis gas stream as the acid gas-depleted product gas stream (38).
• the synthesis gas stream (50) and the gaseous hydrocarbon product stream (84) (or derivative streams resulting from intermediate treatment) are co-processed in an acid gas removal unit (200) to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present), and generate the acid gas-depleted product gas steam (38), which can be a single stream generated from a combination of, or individual stream derived from, the synthesis gas stream (50) and the gaseous hydrocarbon product stream (84) (or derivative streams resulting from intermediate treatment).
• an acid gas removal unit (200) to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present)
• the acid gas-depleted product gas steam (38) can be a single stream generated from a combination of, or individual stream derived from, the synthesis gas stream (50) and the gaseous hydrocarbon product stream (84) (or derivative streams resulting from intermediate treatment).
• synthesis gas stream (50) and the gaseous hydrocarbon product stream (84) are co-processed to generate a carbon dioxide-rich stream (87) and a combined acid-gas depleted gaseous hydrocarbon product stream (80) (as acid gas-depleted product gas steam (38)).
• synthesis gas stream (50) and the gaseous hydrocarbon product stream (84) are co-processed to generate a carbon dioxide-rich stream (87), and an individual acid gas-depleted gaseous hydrocarbon product stream (31) and an individual acid gas-depleted synthesis gas stream (30) (acid gas-depleted product gas steam (38)).
• Acid gas removal processes typically involve contacting a gas stream with a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like to generate CO2 and/or FLS laden absorbers.
• a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like to generate CO2 and/or FLS laden absorbers.
• a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like.
• One method can involve the use of Selexol ® (UOP LLC, Des Plaines, IL USA) or Rectisol ® (Lurgi AG, Frankfurt am
• At least a substantial portion (e.g., substantially all) of the CO2 and/or H 2 S (and other remaining trace contaminants) should be removed via the acid gas removal processes.
• “Substantial" removal in the context of acid gas removal means removal of a high enough percentage of the component such that a desired end product can be generated. The actual amounts of removal may thus vary from component to component. Desirably, only trace amounts (at most) of H 2 S should be present in the acid gas-depleted product stream, although higher amounts of CO2 may be tolerable depending on the desired end product.
• At least about 85%, or at least about 90%, or at least about 92%, of the CO2, and at least about 95%, or at least about 98%, or at least about 99.5%, of the H 2 S, should be removed, based on the amount of those components contained in the streams fed to the acid gas removal unit (200).
• Any recovered ELS (88) from the acid gas removal can be converted to elemental sulfur by any method known to those skilled in the art, including the Claus process. Sulfur can be recovered as a molten liquid.
• the carbon dioxide-rich stream (87) resulting from acid gas removal is a sour CO2 stream, as disclosed in previously incorporated US Patent Appln. Ser.
• the synthesis gas stream (50) and the gaseous hydrocarbon stream (84) may be combined at various stages prior to the acid gas removal unit (200) to create a combined gas stream (60) which is fed into acid gas removal unit (200), or the two streams may be combined at some point in the acid gas removal unit (200) and co-processed.
• the resulting acid gas-depleted gaseous hydrocarbon product stream (80) will generally comprise one or both of CH 4 and 3 ⁇ 4, other gaseous hydrocarbons from the gaseous hydrocarbon stream (84), and optionally CO (for the downstream methanation), and typically no more than contaminant amounts of CO 2 , 3 ⁇ 40, I3 ⁇ 4S and other contaminants.
• a carbon dioxide-rich stream (87) is also generated containing a substantial portion of carbon dioxide from both synthesis gas stream (50) and gaseous hydrocarbon stream (84). If one or both of synthesis gas stream (50) and gaseous hydrocarbon stream (84) contain other acid gas contaminants, such as hydrogen sulfide, then an additional stream may be generated, such as hydrogen sulfide stream (88).
• the synthesis gas stream (50) and the gaseous hydrocarbon stream (84) are co-processed in an acid gas removal unit to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present), and generate a carbon dioxide-rich stream (87), an acid gas-depleted gaseous hydrocarbon product stream (31) and an acid gas-depleted synthesis gas stream (30).
• the synthesis gas stream (50) and the gaseous hydrocarbon stream (84) are first individually treated in a second acid gas absorber unit (210) and a first acid gas absorber unit (230), respectively, to generate a separate acid gas-depleted synthesis gas stream (30) and second acid gas-rich absorber stream (35), and a separate acid gas-depleted gaseous hydrocarbon product stream (31) and first acid gas-rich absorber stream (36).
• the resulting acid gas-depleted gaseous hydrocarbon product stream (31) will generally comprise CH 4 and other gaseous hydrocarbons from the gaseous hydrocarbon stream (84), and typically no more than contaminant amounts of CO 2 , 3 ⁇ 40, I3 ⁇ 4S and other contaminants.
• the resulting acid gas-depleted synthesis gas stream (30) will generally comprise one or both of CH 4 and 3 ⁇ 4, and optionally CO (for the downstream methanation), and typically no more than contaminant amounts of CO 2 , H 2 O, I3 ⁇ 4S and other contaminants.
• the resulting acid gas-depleted gaseous hydrocarbon product stream (31) and an acid gas-depleted synthesis gas stream (30) may be co-processed or separately processed as described further below.
• first acid gas-rich absorber stream (36) and second acid gas-rich absorber stream (35) are co-processed in an absorber regeneration unit (250) to ultimately result in an acid gas stream containing the combined acid gases (and other contaminants) removed from both synthesis gas stream (50) and gaseous hydrocarbon stream (84).
• First acid gas-rich absorber stream (36) and second acid gas-rich absorber stream (35) may be combined prior to or within absorber regeneration unit (250) for co-processing.
• An acid gas- lean absorber stream (70) is generated, which can be recycled back to one or both of first acid gas absorber unit (230) and second acid gas absorber unit (210) along with make-up absorber as required.
• a carbon dioxide-rich stream (87) is also generated containing a substantial portion of carbon dioxide from both synthesis gas stream (50) and gaseous hydrocarbon stream (84). If one or both of synthesis gas stream (50) and gaseous hydrocarbon stream (84) contain other acid gas contaminants, such as hydrogen sulfide, then an additional stream may be generated, such as hydrogen sulfide stream (88).
• carbon dioxide-rich stream (87) is used for EOR.
• the recovered carbon dioxide-rich recycle stream (87) is in whole or in part compressed via compressor (400) to generate pressurized carbon dioxide stream (89) for the EOR portion of the process.
• a CO 2 product stream (90) can also optionally be split off of pressurized carbon dioxide stream (89).
• Suitable compressors for compressing carbon dioxide-rich recycle stream (87) to appropriate pressures and conditions for EOR are in a general sense well-known to those of ordinary skill in the relevant art.
• Non-limiting options are discussed below in reference to Figures 3 and 5. Although Figures 3 and 5 only depict some of the options as applied to acid gas-depleted gaseous hydrocarbon product stream (80) and acid gas-depleted synthesis gas stream (30), these options (and others) may be applied to acid gas-depleted gaseous hydrocarbon product stream (31) (or a combined stream) where appropriate.
• Hydrogen may be separated from all or a portion of the acid gas-depleted gaseous hydrocarbon product stream (80) or acid gas-depleted synthesis gas stream (30) according to methods known to those skilled in the art, such as cryogenic distillation, the use of molecular sieves, gas separation (e.g., ceramic or polymeric) membranes, and/or pressure swing adsorption (PSA) techniques.
• cryogenic distillation the use of molecular sieves, gas separation (e.g., ceramic or polymeric) membranes, and/or pressure swing adsorption (PSA) techniques.
• gas separation e.g., ceramic or polymeric membranes
• PSA pressure swing adsorption
• a PSA device is utilized for hydrogen separation.
• PSA technology for separation of hydrogen from gas mixtures containing methane (and optionally carbon monoxide) is in general well-known to those of ordinary skill in the relevant art as disclosed, for example, in US6379645 (and other citations referenced therein).
• PSA devices are generally commercially available, for example, based on technologies available from Air Products and Chemicals Inc. (Allentown, PA), UOP LLC (Des Plaines, IL) and others.
• a hydrogen membrane separator can be used followed by a PSA device.
• Such separation provides a high-purity hydrogen product stream (72) and a hydrogen-depleted gas stream (74).
• the recovered hydrogen product stream (72) preferably has a purity of at least about 99 mole%, or at least 99.5 mole%, or at least about 99.9 mole%.
• the recovered hydrogen can be used, for example, as an energy source and/or as a reactant.
• the hydrogen can be used as an energy source for hydrogen-based fuel cells, or for power and/or steam generation, for example, in power block (760).
• the hydrogen can also be used as a reactant in various hydrogenation processes, such as found in the chemical and petroleum refining industries.
• the hydrogen-depleted gas stream (74) will substantially comprise light hydrocarbons, such as methane, with optional minor amounts of carbon monoxide (depending primarily on the extent of the sour shift reaction and bypass), carbon dioxide (depending primarily on the effectiveness of the acid gas removal process) and hydrogen (depending primarily on the extent and effectiveness of the hydrogen separation technology), and can be further processed/utilized as described below.
• light hydrocarbons such as methane
• carbon monoxide depending primarily on the extent of the sour shift reaction and bypass
• carbon dioxide depending primarily on the effectiveness of the acid gas removal process
• hydrogen depending primarily on the extent and effectiveness of the hydrogen separation technology
• the acid gas-depleted gaseous hydrocarbon product stream (80) or the acid gas- depleted synthesis gas stream (30) (or the hydrogen-depleted sweetened gas stream (74)) contains carbon monoxide and hydrogen, all or part of the stream may be fed to a (trim) methanation unit (740) to generate additional methane from the carbon monoxide and hydrogen (see formula (III) above), resulting in a methane-enriched gas stream (75).
• the methanation reaction can be carried out in any suitable reactor, e.g., a single- stage methanation reactor, a series of single-stage methanation reactors or a multistage reactor.
• Methanation reactors include, without limitation, fixed bed, moving bed or fluidized bed reactors. See, for instance, US3958957, US4252771, US3996014 and US4235044.
• Methanation reactors and catalysts are generally commercially available.
• the catalyst used in the methanation, and methanation conditions are generally known to those of ordinary skill in the relevant art, and will depend, for example, on the temperature, pressure, flow rate and composition of the incoming gas stream.
• the methane-enriched gas stream (75) may be, for example, further provided to a heat exchanger unit (750). While the heat exchanger unit (750) is depicted as a separate unit, it can exist as such and/or be integrated into methanation unit (740), thus being capable of cooling the methanation unit (740) and removing at least a portion of the heat energy from the methane-enriched stream (75) to reduce the temperature and generate a cooled methane-enriched stream (76).
• the recovered heat energy can be utilized, for example, to generate a process steam stream from a water and/or steam source.
• All or part of the methane-enriched stream (75) can be recovered as a methane product stream (77) or, it can be further processed, when necessary, to separate and recover CH 4 by any suitable gas separation method known to those skilled in the art including, but not limited to, cryogenic distillation and the use of molecular sieves or gas separation (e.g., ceramic) membranes.
• the acid gas-depleted hydrocarbon stream (80), or the acid gas-depleted synthesis gas stream (30), or the acid gas-depleted gaseous hydrocarbon product stream (31), or a combination of the acid gas-depleted synthesis gas stream (30) and the acid gas-depleted gaseous hydrocarbon product stream (31), or the hydrogen-depleted gas stream (74), and/or the methane-enriched gas stream (75), are "pipeline-quality natural gas”.
• a "pipeline-quality natural gas” typically refers to a natural gas that is (1) within ⁇ 5 % of the heating value of pure methane (whose heating value is 1010 btu/ft 3 under standard atmospheric conditions), (2) substantially free of water (typically a dew point of about -40°C or less), and (3) substantially free of toxic or corrosive contaminants.
• All or a portion of the aforementioned streams can, for example, be utilized for combustion and/or steam generation, for example, in a power generation block (760) to produce electrical power (79) which may be either utilized within the plant or can be sold onto the power grid.
• All or a portion of these streams can also be used as a recycle hydrocarbon stream (78), for example, for use as carbonaceous feedstock (10) in a gaseous partial oxidation/methane reforming process, or for the generation of syngas feed stream (12) for use in a hydromethanation process (in, for example, a gaseous partial oxidation/methane reforming process). Both of these uses can, for example, ultimately result in an optimized production of hydrogen product stream (72), and carbon dioxide-rich stream (87).
• the present process can be integrated with a power generation block (760, 760a) for the production of electrical power (79, 79a) as a product of the integrated process.
• the power generation block (760, 760a) can be of a configuration similar to that generally utilized in integrated gasification combined cycle (IGCC) applications.
• the power generation block (760, 760a) can comprise an air separation unit (800a) for use in generating oxygen-rich stream (14) and nitrogen-rich stream (17) from an air stream (18).
• FIG. 6 An example of a power generation block suitable for use in connection with the present invention is depicted in Figure 6. Reference is made to power generation block (760) in Figure 6 and below, but the discussion is also applicable to power generation block (760a) as well.
• a combustible gas stream (81) is fed into power generation block (760).
• Combustible gas stream (81) is typically a methane-rich and/or hydrogen-rich gas stream, such as a natural or synthetic natural gas stream.
• combustible gas stream (81) can comprise all or a portion of one or more of (i) acid-gas depleted product gas stream (38); (ii) acid-gas depleted gaseous hydrocarbon product stream (31), (iii) acid gas- depleted hydrocarbon product stream (80); and/or (iv) a downstream derivative of (i), (ii) and/or (iii), such as hydrogen product stream (72), hydrogen-depleted gas stream (74) and/or methane-enriched gas stream (76).
• power generation blocks (760) and (760a) can be present.
• the combustible gas stream (81) is gaseous hydrocarbon stream (84).
• Power generation block (760a) if present can have the same or different configuration as power generation block (760).
• combustible gas stream (81) can initially be fed to an expander (987), which can be a first turbine generator.
• a first electrical power stream (79b) can be generated as a result of this decompression.
• the decompressed combustible gas stream can then be fed to a combustor (980) along with a compressed air stream (not depicted) or a compressed oxygen-rich stream (14b), where it is combusted to produce combustion gases (83) at an elevated temperature and pressure.
• compressed oxygen-rich stream (14b) comprises at least a portion of oxygen-rich stream (14).
• Suitable combustors are generally well-known to those of ordinary skill in the relevant art.
• the resulting combustion gases (83) are fed to a second turbine generator (982) where a second electrical power stream (79c) is generated.
• the second turbine generator (982) can be coupled (mechanically and/or electrically) to a compressor for compressing, for example, an air stream (18) to generate compressed air stream for use in combustor (980).
• compressor is air separation unit (800a) into which air stream (18) is fed, and oxygen-rich stream (14) and nitrogen-rich stream (17) are generated.
• air separation unit (800) is operated utilizing electrical power (79) generated in power generation block (760).
• stack gas stream (96) will comprise substantially CO 2 and can optionally be processed via acid gas removal unit (200) to capture the carbon dioxide, or directly provided to a compressor (such as compressor (400)) for EOR use.
• a steam stream (91) generated in heat recovery steam generator (985) can be passed to a third turbine generator (985) where a third electrical power stream (79d) is generated.
• a steam/water stream (98) from third turbine generator (985) is then passed back to heat recovery steam generator (984) for reheating and reuse.
• stack gas stream (96) will comprise substantially steam which can be recovered and utilized in the process, for example, directly fed to third turbine generator (985) for the generation of electrical power.
• Air separation units suitable for use as air separation unit (800) and (800a) are in general well-known to those of ordinary skill in the relevant art.
• Well-know air separation technologies include, for example, cryogenic distillation, ambient temperature adsorption and membrane separations.
• the nitrogen-rich stream (17) is in whole or in part compressed via compressor (410) to generate pressurized nitrogen stream (19) for the EOR portion of the process.
• Suitable compressors for compressing nitrogen-rich stream (17) to appropriate pressures and conditions for EOR are in a general sense well-known to those of ordinary skill in the relevant art.
• the synthesis gas stream is produced by a catalytic steam methane reforming process utilizing a methane-containing stream as the carbonaceous feedstock.
• the synthesis gas stream is produced by a non-catalytic (thermal) gaseous partial oxidation process utilizing a methane-containing stream as the carbonaceous feedstock.
• the synthesis gas stream is produced by a catalytic autothermal reforming process utilizing a methane-containing stream as the carbonaceous feedstock.
• the methane-containing stream for use in these processes may be a natural gas stream, a synthetic natural gas stream or a combination thereof.
• the methane-containing stream comprises all or a portion of the acid gas-depleted gaseous hydrocarbon product stream (or a derivative of this stream after downstream processing).
• the resulting synthesis gas stream from these processes will comprise at least hydrogen and one or both of carbon monoxide and carbon dioxide, depending on gas processing prior to acid gas removal.
• the synthesis gas stream is produced by a non-catalytic thermal gasification process utilizing a non-gaseous carbonaceous material as the carbonaceous feedstock, such as coal, petcoke, biomass and mixtures thereof.
• the resulting synthesis gas stream from this process will comprise at least hydrogen and one or both of carbon monoxide and carbon dioxide, depending on gas processing prior to acid gas removal.
• the synthesis gas stream is produced by a catalytic hydromethanation process utilizing a non-gaseous carbonaceous material as the carbonaceous feedstock, such as coal, petcoke, biomass and mixtures thereof.
• a non-gaseous carbonaceous material such as coal, petcoke, biomass and mixtures thereof.
• the resulting synthesis gas stream from this process will comprise at least methane, hydrogen and carbon dioxide, and optionally carbon monoxide, depending on gas processing prior to acid gas removal.

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