US20130251598A1 - Carbon removal from an integrated thermal recovery process - Google Patents
Carbon removal from an integrated thermal recovery process Download PDFInfo
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- US20130251598A1 US20130251598A1 US13/894,554 US201313894554A US2013251598A1 US 20130251598 A1 US20130251598 A1 US 20130251598A1 US 201313894554 A US201313894554 A US 201313894554A US 2013251598 A1 US2013251598 A1 US 2013251598A1
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Definitions
- the present invention relates generally to a method and means of removing a portion of carbon from natural gas used to provide steam and electrical power for a large hydrocarbon thermal recovery plant.
- Non-conventional means include drilling wells and pumping crude oil or natural gas to the surface.
- Non-conventional means include recovering bitumen and heavy oil by, for example, thermal stimulation or mining. Producers, especially of some of the non-conventional means which generate significant additional fossil carbon dioxide during recovery and upgrading, are becoming more and more regulated as the link between carbon dioxide emissions and global warming becomes understood.
- SAGD Steam Assisted Gravity Drain
- CSS Cyclical Steam Stimulation
- bitumen is recovered, and the bitumen is separated from the recovered water.
- the water is treated so that it can be used to produce steam in boilers.
- Diluents are added to the bitumen so that it can be transported by pipeline.
- Steam is produced primarily by using a fossil fuel energy source such as natural gas, coal, a fuel derived from bitumen and the like. These operations require substantial amounts of energy, much of which is wasted. These operations also generate large amounts of carbon dioxide when producing steam and electrical power and this carbon dioxide is usually released into the atmosphere.
- Producing regions such as the Western Canadian Sedimentary Basin are increasingly coming under regulatory pressures to reduce emissions of fossil carbon dioxide, wherein each producer is given the choice of reducing its carbon dioxide emissions, trading for carbon credits or paying a carbon tax.
- a producer may choose to reduce their fossil carbon dioxide emissions by installing on-site carbon capture and sequestration facilities.
- trading for carbon credits or paying a carbon tax is a less costly and, in the short term, a less risky course of action.
- the various embodiments and configurations of the present invention are directed generally to a process of removing a portion of carbon from natural gas used to generate steam and electrical power e power for a for a hydrocarbon thermal recovery plant, such as for example a SAGD or CSS plant.
- a process comprising the steps: (a) receiving a gas stream comprising primarily methane; (b) removing a first portion of the gas stream from a second portion of the gas stream; (c) converting the first portion of the gas stream to produce a reformed and water-gas shifted gas comprising primarily carbon dioxide and molecular hydrogen; (d) removing, from the reformed and water-gas shifted gas, at least most of the carbon dioxide to form a product gas; and (e) thereafter combining the product gas with the second portion of the gas stream to form a mixed gas, whereby a carbon content of the mixed gas is reduced relative to the received gas stream.
- a system comprising: an input to receive a gas stream comprising primarily methane; a gas separator to remove a first portion of the gas stream from a second portion of the gas stream; a steam methane reformer reactor to convert the first portion of the gas stream to a reformed gas comprising primarily molecular hydrogen and carbon monoxide; a water-gas shift reactor to convert the reformed gas into a reformed and water-gas shifted gas comprising primarily carbon dioxide and molecular hydrogen; a carbon separator to remove, from the reformed and water-gas shifted gas, at least most of the carbon dioxide to form a product gas; and a gas combiner to combine the product gas with the second portion of the gas stream to form a mixed gas, whereby a carbon content of the mixed gas is reduced relative to the received gas stream.
- a method/system that perform the following steps/operations: (a) forming, from an input gas stream comprising primarily methane, an intermediate gas stream comprising primarily gas-phase molecular hydrogen and carbon oxide; (b) contacting the intermediate gas stream with an alkali and/or alkaline earth metal oxide to form a second intermediate gas stream comprising molecular hydrogen and carbonates; (c) removing at least most of the molecular hydrogen from the second intermediate gas stream to form a product gas stream comprising primarily molecular hydrogen and a third intermediate gas stream comprising at least most of the carbonates; (d) converting, using heat from the forming step (a), at least most of the carbonates in the third intermediate gas stream to gas-phase carbon oxide and alkali and/or alkaline earth metal oxide; (e) removing at least most of the gas-phase carbon oxide from the alkali and/or alkaline earth metal oxide; and (f) recycling the separated alkali and/or alkaline earth metal oxide to step (
- the product gas comprises no more than about 25% of the carbon present in the input gas stream.
- the various embodiments can have a number of advantages.
- the embodiments can reduce significantly fossil carbon emissions from fossil fuels.
- the embodiments can convert fossil carbon into carbon dioxide for sequestration.
- the resulting molecular hydrogen is itself a fuel.
- the embodiments can significantly reduce, relative to conventional processes, energy waste. By using energy more efficiently, heavy oil deposits may be exploited more inexpensively.
- Calcination is a thermal treatment process applied to ores and other solid materials in order to bring about a thermal decomposition, phase transition, or removal of a volatile fraction.
- the calcination process normally takes place at temperatures below the melting point of the product materials. Calcination takes place in the absence of air.
- the process of calcination derives its name from its most common application, the decomposition of calcium carbonate (limestone) to calcium oxide (lime).
- a carbon sequestration facility is a facility in which carbon dioxide can be controlled and sequestered in a repository such as for example a mature or depleted oil and gas reservoir, an unmineable coal seam, a deep saline formation, a basalt formation, a shale formation, or an excavated tunnel or cavern.
- a repository such as for example a mature or depleted oil and gas reservoir, an unmineable coal seam, a deep saline formation, a basalt formation, a shale formation, or an excavated tunnel or cavern.
- Dilbit is short for diluted bitumen.
- dilbit is about 65% bitumen diluted with about 35% naphtha.
- the naphtha is added to make a fluid that can be transported by pipeline by reducing the viscosity of the bitumen/naphtha mixture.
- the dilbit can be transported by pipeline to a refinery.
- the naphtha diluent can be taken out as a straight run naphtha/gasoline and reused as diluent. Or it is processed to products in the refinery.
- the dilbit has a lot of light hydrocarbons from the diluent and a lot of heavy hydrocarbons from the bitumen. So it is a challenge to process directly in a normal refinery. Dilbit can only be a small part of a normal refinery's total crude slate.
- condensate can also be used as diluent.
- a duct burner as used herein is any industrial combustor or burner that is operated at close to ambient pressure.
- HRSG stands for Heat Recovery Steam Generator.
- a heat recovery steam generator or HRSG is a heat exchange apparatus that recovers heat from a hot gas stream to produce steam.
- the hot gas stream can be provided, for example, by the hot exhaust from a gas turbine.
- a hydrocarbon transport means as used herein includes any means of bulk hydrocarbon transport including but not limited to a pipeline, a train of tank cars or gondolas, a ship, a barge or a truck convoy.
- a mobilized hydrocarbon is a hydrocarbon that has been made flowable by some means.
- some heavy oils and bitumen may be mobilized by heating them or mixing them with a diluent to reduce their viscosities and allow them to flow under the prevailing drive pressure.
- Most liquid hydrocarbons may be mobilized by increasing the drive pressure on them, for example by water or gas floods, so that they can overcome interfacial and/or surface tensions and begin to flow.
- Natural gas refers to a hydrocarbon gas including low molecular weight hydrocarbons, primarily methane.
- the low molecular weight hydrocarbons commonly include, in addition to methane, ethane, propane, and butane.
- a typical natural gas-containing product contains from about 50 to about 98 mole percent methane, from about 1 to about 15 mole percent ethane, and up to about 5 mole percent propane and butane.
- the product may contain various sulfur, nitrogen and carbon dioxide compounds as contaminants.
- Pipeline quality natural gas is specified for example by the American Gas Association and Canadian Gas Association. Typically, there are limits on sulphur, carbon dioxide, water and other constituents of natural gas obtained from nature to comply with pipeline specifications.
- Primary production or recovery is the first stage of hydrocarbon production, in which natural reservoir energy, such as gas-drive, water-drive or gravity drainage, displaces hydrocarbons from the reservoir, into the wellbore and up to surface.
- Natural reservoir energy such as gas-drive, water-drive or gravity drainage
- Secondary production or recovery methods frequently involve an artificial-lift system and/or reservoir injection for pressure maintenance.
- the purpose of secondary recovery is to maintain reservoir pressure and to displace hydrocarbons toward the wellbore.
- Tertiary production or recovery is the third stage of hydrocarbon production during which sophisticated techniques that alter the original properties of the oil are used.
- Enhanced Oil Recovery can begin after a secondary recovery process or at any time during the productive life of an oil reservoir. Its purpose is not only to restore formation pressure, but also to improve oil displacement or fluid flow in the reservoir.
- the three major types of enhanced oil recovery operations are chemical flooding, miscible displacement and thermal recovery.
- a producer is a any producer of natural gas, oil, heavy oil, bitumen, peat or coal from a hydrocarbon reservoir.
- Reforming means fossil fuel reforming which is a method of producing useful products, such as hydrogen or ethylene from fossil fuels.
- Fossil fuel reforming is done through a fossil fuel processor or reformer.
- the most common fossil fuel processor is a steam reformer. This conversion is possible as hydrocarbons contain much hydrogen.
- the most commonly used fossil fuels for reforming today are methanol and natural gas, yet it is possible to reform other fuels such as propane, gasoline, autogas, diesel fuel, methanol and ethanol. During the conversion, the leftover carbon dioxide is typically released into the atmosphere.
- reforming is the dominant method for producing hydrogen.
- the basic chemical reaction for reforming is:
- This reaction is endothermic.
- the produced carbon monoxide can combine with more steam to produce further hydrogen via the water gas shift reaction.
- Synbit is a blend of bitumen and synthetic crude.
- Synthetic crude is a crude oil product produced, for example, by the upgrading and refining of bitumen or heavy oil.
- synbit is about 50% bitumen diluted with about 50% synthetic crude.
- Syngas (from synthesis gas) is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen.
- Examples of production methods include steam reforming of natural gas or liquid hydrocarbons to produce hydrogen, the gasification of coal and in some types of waste-to-energy gasification facilities. The name comes from their use as intermediates in creating synthetic natural gas and for producing ammonia or methanol.
- Syngas is also used as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via Fischer-Tropsch synthesis and previously the Mobil methanol to gasoline process.
- Syngas consists primarily of hydrogen, carbon monoxide, and very often some carbon dioxide, and has less than half the energy density of natural gas. Syngas is combustible and often used as a fuel source or as an intermediate for the production of other chemicals.
- Upgrading means removing carbon atoms from a hydrocarbon fuel, replacing the removed carbon atoms with hydrogen atoms to produce an upgraded fuel and then combining the carbon atoms with oxygen atoms to form carbon dioxide.
- the water-gas shift reaction is a chemical reaction in which carbon monoxide reacts with water to form carbon dioxide and hydrogen:
- the water-gas shift reaction is often used in conjunction with steam reforming of methane or other hydrocarbons.
- the water-gas shift reaction is slightly exothermic, yielding 42 kJ per mole.
- the process is often used in two stages, stage one a high temperature shift at 350° C. and stage two, a low temperature shift at 190 to 210° C.
- a reference to oil herein is intended to include low API hydrocarbons such as bitumen (API less than ⁇ 10°) and heavy crude oils (API from ⁇ 10° to ⁇ 20°) as well as higher API hydrocarbons such as medium crude oils (API from ⁇ 20° to ⁇ 35°) and light crude oils (API higher than ⁇ 35°).
- bitumen is also taken to mean a reference to low API heavy oils.
- At least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation.
- each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
- FIG. 1 is a schematic showing the principal elements of a typical prior art SAGD operation using natural gas for power.
- FIG. 2 is schematic of the present invention showing the principal elements of an integrated SAGD operation using natural gas for power.
- FIG. 3 is a schematic of the present invention showing the principal elements of the innovative portion of an integrated SAGD operation of FIG. 2 .
- FIG. 4 is a partial schematic of FIG. 3 highlighting fuel and other gas pathways.
- FIG. 5 is a partial schematic of Figure highlighting water and steam pathways.
- FIG. 6 is a schematic of a pre-combustion CO 2 capture process.
- FIG. 7 is schematic of the present invention showing the principal elements of the innovative portion of an integrated SAGD operation with the pre-combustion CO 2 capture process of FIG. 6 .
- natural gas is used as the primary energy source but a first portion of the natural gas is reformed to produce carbon dioxide and hydrogen in a carbon extraction plant integrated into a main bitumen process plant.
- the carbon dioxide is liquified and can be sequestered, used for EOR operations, sold or otherwise controlled such that it is not released into the atmosphere.
- the hydrogen is mixed with a second portion of the natural gas to produce a high energy fuel for operating other apparatuses in the plant.
- This removal of a portion of carbon from the emissions requires some additional energy but the plant is configured in such a way as to utilize as much waste heat as possible so that the overall plant processes more bitumen and releases less carbon dioxide for about the same energy consumption as a conventional SAGD operation. As a result the plant operator may be eligible for a carbon credit or at least a reduced carbon tax.
- carbon dioxide is removed pre-combustion by well known processes such as for example the Selexol process.
- carbon dioxide is removed pre-combustion by a fluidized bed reactor approach and carbon dioxide is removed from the sorbent by heat generated in the steam methane reformer reactor.
- FIG. 1 is a schematic showing the principal elements of a typical prior art SAGD operation using natural gas for power.
- 30,000 barrels per day (“bpd”) of bitumen are processed using approximately 34 million standard cubic feet per day of natural gas as fuel. This translates to 1,133 standard cubic feet per day of natural gas burned to process a barrel of bitumen.
- the eventual product of this plant is a 19° to 20° API dilbit.
- bitumen recovered from a SAGD operation is shipped to a refinery for upgrading. If shipment is made by pipeline, a diluent must be added to the bitumen to allow the blend to flow.
- recovered bitumen is partially upgraded to an approximately 20° API product which can then be transported by pipeline to a refinery.
- raw bitumen-water feedstock from a well pad facility 102 is fed into a bitumen-water separation sequence comprising a Free Water Knock-Out (“FWKO”) unit 103 .
- Diluent 106 is added to the raw bitumen-water feedstock to form a pumpable mixture prior to entering the FWKO unit 103 .
- the FWKO unit 103 separates most of the diluent-bitumen mixture (“dilbit”). This dilbit mixture is then sent to an oil treatment unit 104 which separates the remaining water from the dilbit.
- Additional diluent 107 is added to the dilbit product which is then sent to a product storage tank 105 , where it remains ready, for example, for transport by pipeline 108 to an upgrader.
- the water from the oil treatment unit 104 is sent to a de-oiling unit 110 for final cleaning of remaining oil residue.
- the oil residue from the de-oiling unit 110 is returned to the feedstock of the FWKO unit 103 .
- Make-up water 116 from a water well source is added to the de-oiled water and then fed to a series of water treatment apparatuses which purify the water in preparation for making steam.
- the water treatment apparatuses are typically comprised of water softener units 111 , walnut filter unit 114 and an ion exchange unit 115 .
- the treated water is fed to steam generators 121 which are used to produce primarily hot dry steam which is sent to a high pressure steam separator unit 122 .
- Natural gas 123 is used to power the steam generators 121 .
- These steam generators may be large single pass boilers or they may be multi-pass drum steam generators.
- about 2,700 tons per day of CO 2 is released 125 into the atmosphere by the drum steam generators 121 which is about 0.09 tons CO 2 released per barrel of bitumen processed.
- the high pressure steam separator unit 122 compresses the steam from the steam generators 121 and delivers the hot, high-pressure, high-quality steam to the well pads 102 for injection into the bitumen reservoir 101 where it is used to continue the bitumen mobilization and recovery process. Condensate ( ⁇ 1 to 2% of the steam) from the high pressure steam separator unit 122 is handled by a blowdown apparatus 124 and sent to a water disposal well 126 .
- FIG. 2 is schematic of the present invention showing the principal elements of an integrated SAGD operation using natural gas for power.
- Natural gas fuel 221 is brought into the facility and a substantial fraction of the natural gas is diverted by a gas separator and reformed and water-gas shifted in a carbon extraction plant to eliminate carbon in the form of captured carbon dioxide (“CO 2 ”).
- CO 2 captured carbon dioxide
- FIG. 3 an innovation is the addition of a carbon extraction plant that modifies a portion of the natural gas fuel input to the main plant.
- the carbon extraction plant delivers clean CO 2 , molecular hydrogen and electrical power.
- the molecular hydrogen is then mixed by a gas combiner with portion of natural gas not sent to the carbon extraction plant to form a mixed gas fuel which is then used to power steam generators and other apparatuses in the main plant.
- a gas combiner with portion of natural gas not sent to the carbon extraction plant to form a mixed gas fuel which is then used to power steam generators and other apparatuses in the main plant.
- at least about 20% of the methane by volume, more typically about 40% of the methane by volume, and as high as about 60% of the methane by volume of the natural gas is converted into molecular hydrogen.
- this use of mixed fuel commonly reduces fossil carbon emissions by at least about 20% and as high as about 60%.
- bitumen 40,000 barrels per day (“bpd”) of bitumen are processed using approximately 42 million standard cubic feet per day of natural gas as fuel 221 . This translates to 1,050 standard cubic feet per barrel of bitumen or slightly more efficient than the prior art plant described in FIG. 1 .
- bpd barrels per day
- only 26 million standard cubic feet per day of natural gas are burned since 16 million standard cubic feet per day of natural gas are reformed and water-gas shifted to remove carbon.
- only 650 standard cubic feet of natural gas is burned to process a barrel of bitumen.
- the remaining energy required to operate the plant is obtained from molecular hydrogen (“H 2 ”) generated by the reforming and water-gas shift processes.
- H 2 molecular hydrogen
- the reforming and water-gas shift processes also generate 31 million standard cubic feet per day of CO 2 which is captured, purified and compressed to 1,000 psi.
- the bitumen product is a 19° to 20° API dilbit which is the same as that of the prior art plant described in FIG. 1 .
- the raw feedstock for the process of the present invention is bitumen or heavy oil recovered by a mining or in-situ operation.
- An example of a mining operation would be a hydraulic mining operation which produces an oil sand slurry.
- An example of hydraulic mining conducted from an underground workspace is disclosed in U.S. Provisional Patent Application No. 60/867,010 entitled “Recovery of Bitumen by Hydraulic Excavation” to Brock, Squires, Watson and filed Nov. 22, 2006 which is incorporated herein by this reference.
- the bitumen, water and sand from a hydraulic mining operation can be separated, for example, by hydrocyclone methods. An example of this method of separation is disclosed in U.S. Pat. No. 7,128,375 issued Oct. 31, 2006, entitled “A Method and Means for Recovering Hydrocarbons from Oil Sands by Underground Mining” to Watson also which is incorporated herein by this reference.
- SAGD Steam Assisted Gravity Drain
- An example of an in-situ recovery operation is a Steam Assisted Gravity Drain (“SAGD”) operation which produces a product stream of water, hot bitumen and gas.
- SAGD operations can be carried out from a surface facility or from an underground workspace.
- An example of this latter approach is disclosed in U.S. patent application Ser. No. 11/441,929 entitled “Method for Underground Recovery of Hydrocarbons” to Brock, Kobler and Watson, filed May 26, 2006.
- a SAGD steam chamber 200 is the reservoir or source of bitumen, condensed water along with dissolved and free gases such as CH 4 , CO 2 , H 2 S and other trace gases.
- the source material is recovered from the steam chamber 200 by producer wells such as used, for example, in SAGD or CSS, or by non-thermal processes such as VAPEX or by a combination of these processes that can cause the bitumen to be mobilized and recovered.
- the produced source material is then sent to an underground location 201 for storage and processing or for storage, pumping to the surface and processing.
- the process of the present invention may be carried out on the surface, underground or portions of the process may be carried out underground. While the producer well-heads are assumed to be underground for purposes of the present illustration, the well heads may be located on the surface.
- One of the products of the process of the present invention is hot, dry, pressurized steam which may be returned to the underground location and finally to the reservoir 200 for ongoing steaming (SAGD or CSS) operations.
- Other products of the process of the present invention such as for example, CO 2 , NO x and SO 2 , may also be captured and returned to the underground location and finally to the reservoir 200 or other geologic repository for sequestration.
- the raw bitumen-water feedstock from underground storage 201 is fed into a bitumen-water separation sequence comprising a Free Water Knock-Out (“FWKO”) unit 203 .
- Diluent 202 is added to the raw bitumen-water feedstock to form a pumpable mixture prior to entering the FWKO unit 203 .
- the de-oiled bitumen-diluent mixture from the FWKO unit 203 is fed to an oil treating unit 204 where at least most of the residual water is removed and added to the input of the water de-oiling unit 208 .
- the treated hydrocarbon mixture, typically, dilbit is sent to a product storage tank 205 .
- Additional diluent 206 is added to the dilbit product so that it can be transported by pipeline 207 to an upgrader.
- bitumen recovery operation typically about 55,000 bpd of 19° to 20° API dilbit is produced, the exact amount of dilbit produced being a function of the API grade of the recovered bitumen.
- the FWKO unit 203 separates most of the water which is then sent to a de-oiling unit 208 for final cleaning of remaining oil residue.
- the oil residue from the de-oiling unit 208 is returned to the feedstock of the FWKO unit 203 .
- Make-up water from a water well source 209 for example, is added to the de-oiled water and then fed to a tube evaporator 210 which distills the water in preparation for making steam. Some water is condensed in the tube evaporator 210 and is processed by a blowdown treatment apparatus 215 and then returned to the ground via a water disposal well 216 . It is understood that reference to a tube evaporator may mean a rising tube evaporator or a falling tube evaporator since both accomplish the same function in process of the present invention.
- bitumen recovery operation from about 80,000 to about 150,000 bpd of water may be recovered. Most of this is condensate when a thermal process such as SAGD is used. Typically there is on the order of about 100 to 125 kg of connate water and on the order of about 200 to 300 kilograms bitumen recovered for every cubic meter of in-situ deposit mobilized.
- an amount of make-up water from the water well source 209 is added to the de-oiled water prior to being fed to the tube evaporator 210 .
- the amount of make-up water is in the range of about 5% to about 15% of the amount of water recovered from the SAGD operation.
- the distilled water from the tube evaporator 210 is fed to the steam drum generators 212 which are used to produce primarily hot dry steam which is sent to a high pressure steam separator unit 213 .
- a mixture of molecular hydrogen and methane (called a mixed gas) are used to power the steam drum generators 212 as described below.
- the primary function of the steam drum generators 212 is to produce high quality steam which is transferred to a high pressure steam separator unit 224 .
- the high pressure steam separator unit 213 compresses the steam from the steam drum generators 212 and delivers the hot, high-pressure, high-quality steam to the underground facility 200 for subsequent use in maintaining temperature and pressure conditions in steam chamber. Water condensate from the high pressure steam separator unit 213 is returned to the tube evaporator 210 .
- natural gas fuel 221 is brought into the facility and a substantial fraction of the natural gas is diverted and reformed and water-gas shifted to eliminate carbon in the from of captured carbon dioxide (“CO 2 ”) in a carbon extraction plant 214 .
- a portion of input natural gas 221 is diverted through the carbon extraction plant 214 and hydrogen 228 is output and mixed with the natural gas that by-passes the carbon extraction plant 214 , to form a mixed gas which is typically about 40% molecular hydrogen and about 60% natural gas by volume.
- the amount of the natural gas fuel diverted through the plant 214 depends on the application and local carbon emission regulations and the mixed gas may vary in composition from about 20% to about 60% molecular hydrogen by volume, corresponding to about 80% to about 40% natural gas by volume.
- the carbon extraction plant 214 is also referred to as a Power-SMR-Steam unit (SMR stands for Steam Methane Reformer).
- the first step of the SMR process involves methane reacting with steam at 850° C. or above to produce a synthesis gas (syngas), a mixture primarily made up of molecular hydrogen (H 2 ) and carbon monoxide (CO).
- a synthesis gas syngas
- H 2 molecular hydrogen
- CO carbon monoxide
- the second step known as a water gas shift (WGS) reaction
- WGS water gas shift
- the carbon monoxide produced in the first reaction is reacted with steam over a catalyst to form molecular hydrogen and carbon dioxide (CO 2 ).
- This process can be accomplished in a high temperature shift reactor at about 350° C. or in a low temperature shift reactor at about 190° C. to about 210° C.
- more than about 90% of the carbon monoxide is typically converted to carbon dioxide.
- 42 MMSCFD of natural gas enters the plant and 16 million standard cubic feet per day (about 38%) is diverted to carbon extraction plant 214 .
- the carbon extraction plant 214 outputs over 30 million standard cubic feet per day of CO 2 at 1,000 psi; 24 MW of electrical power; around 200,000 lbs per hour of steam and about 64 million standard cubic feet per day of hydrogen.
- the steam is added to the high pressure steam separator 213 ; the 24 MW of power is used to operate the various units in the carbon extraction plant 214 and the main plant; the CO 2 223 is sold, used for EOR or sequestered; and the recovered hydrogen 226 is mixed with the 26 million standard cubic feet per day of natural gas 221 to produce a high energy gas mix that is used in the burners of the steam drum generators 212 .
- the carbon extraction plant 214 removes a substantial portion of fossil carbon while using slightly less energy to process a barrel of bitumen and produce steam than the prior art plant of FIG. 1 .
- bitumen is processed using 42 million standard cubic feet of natural gas and releasing 2,880 tons of CO 2 into the atmosphere.
- 30,000 bpd of bitumen is processed using 34 million standard cubic feet of natural gas and releasing 2,700 tons of CO 2 into the atmosphere.
- the integrated plant of FIG. 2 releases only about 80% the carbon dioxide per barrel of bitumen processed as does the prior art plant of FIG. 1 .
- the integrated plant can release as little as about 70% the carbon dioxide per barrel of bitumen processed as does the prior art plant.
- FIG. 3 is a schematic of the present invention showing a carbon extraction plant (item 214 in FIG. 2 ) which is a principal innovative system of the integrated SAGD operation described in FIG. 2 .
- Natural gas is the fuel for the carbon extraction plant.
- the natural gas is pre-heated to a temperature commonly less than 850° C. (the temperature at which the methane molecules break apart) by two heat exchangers then used as fuel for a steam methane reformer reactor and water-gas shift reactor.
- a steam methane reformer reactor at least most of the methane in the input natural gas stream is converted into molecular hydrogen and carbon monoxide.
- the output of the steam methane reformer 301 ranges from about 25 to about 95 mole percent molecular hydrogen (H 2 ) and from about 5 to about 75 mole percent carbon monoxide (CO).
- the water-gas shift process converts typically at least most and more typically about 90% to about 95% of CO to CO 2 .
- the output of these two processes is CO 2 and H 2 which goes to a CO 2 absorption (or carbon separator) apparatus.
- CO 2 absorption (or carbon separator) apparatus typically, at least about 90% and as much as about 95% of the methane is converted into carbon dioxide and molecular hydrogen by the combined processes.
- a portion of the CO 2 is directed to an electrically powered compressor to create CO 2 for sale, for EOR operations or for delivery to be sequestered.
- a second portion of the H 2 from the CO 2 absorption apparatus is purified. Some of this H 2 may be removed for sale and some is mixed with a portion of natural gas in gas fuel mixer to make a mixed gas fuel. This mixed gas fuel is used to power a combustion turbine, the steam methane reformer, an HRSG facility and the CO 2 absorption apparatus.
- Water is brought in and preheated in the water-gas shift reactor to a temperature ranging from about 50° C. to about 300° C. and then sent to the HRSG facility where steam is produced and sent to a steam bank. Some steam is sent back to the steam generators in the main plant. Some steam is sent to the steam methane reformer, some to the water-gas shift reactor and some to the CO 2 absorption apparatus. Flue gases from the combustion turbine are mixed with fuel and used in a duct burner in the steam methane reformer to power the HRSG facility.
- the amount of the natural gas fuel diverted through the plant 214 depends on the application and local carbon emission regulations and the mixed gas may vary in composition from about 20% to about 60% molecular hydrogen, corresponding to about 80% to about 40% natural gas by volume.
- This mixed gas is used to power a combustion turbine 306 which generates, in this example, about 24 MW of electrical power 361 .
- this mixed gas is also used to power: the steam methane reformer reactor 301 ; a heat recovery steam generator (“HRSG”) 304 which produces steam from water 352 input from the output of the tube evaporator (item 210 in FIG. 2 ) shown in FIG. 2 ; and a CO 2 absorption apparatus 310 .
- HRSG heat recovery steam generator
- the steam from the HRSG is used in the steam methane reformer reactor 301 , water-gas shift reactor 302 and CO 2 absorption apparatus 310 .
- the steam not utilized in the carbon extraction plant is returned to the high pressure steam separator (item 213 in FIG. 2 ) shown in FIG. 2 .
- An electrical motor is used to drive power turbine 1014 which, in turn, drives a compressor 1015 which compresses the carbon dioxide 1037 to about 1,000 psi.
- the remainder of the hydrogen produced 336 is sent out of the carbon extraction plant and mixed with the natural gas that by-passed the carbon extraction plant to form a second mixed gas fuel (typically about 60% natural gas and about 40% hydrogen) that is used in the burners of the steam drum generators (item 212 in FIG. 2 ) shown in FIG. 2 .
- a second mixed gas fuel typically about 60% natural gas and about 40% hydrogen
- Natural gas 331 used as the primary fuel to power the operation, is input as shown. Some of the natural gas 331 is mixed with hydrogen (“H 2 ”) 337 to form a mixed gas fuel 341 . The remainder of the natural gas 331 is sent through a heat exchanger 306 to be heated by the output gases from the water-gas shift reactor 302 and then to pick up more heat from the output gases from the steam methane reformer reactor 301 and is then fed into the steam methane reformer reactor 301 to be combined with steam and reformed into syn gas. Syn gas is carbon monoxide (“CO”) and molecular hydrogen (“H2”) with some carbon dioxide (“CO 2 ”).
- CO carbon monoxide
- H2 molecular hydrogen
- the output of the steam methane reformer reactor 301 is sent to the water-gas shift reactor 302 where it is combined with steam to form primarily carbon dioxide (“CO 2 ”) and molecular hydrogen (“H 2 ”) 332 .
- CO 2 carbon dioxide
- H 2 molecular hydrogen
- In the water-shift reactor 302 typically at least about 80% and more typically at least about 90% of the carbon monoxide is converted into carbon dioxide.
- These gases are then sent to a CO 2 absorption (or carbon separator) apparatus 310 where any of several well-known processes are used to separate the CO 2 and H 2 .
- the H 2 is sent to a purifier 313 where a portion 337 is then used to mix with natural gas to form a mixed gas fuel (typically about 60% natural gas and about 40% hydrogen by volume).
- the remainder is sent back to the main plant ( FIG. 2 ) where it can also be used to form a mixed gas fuel.
- the mixed gas fuel is used to power the steam methane reformer reactor 301 ; a combustion turbine 306 ; a heat recovery steam generator (“HRSG”) 304 ; and a CO 2 absorption apparatus 310 .
- the combustion turbine 306 drives a generator 307 which produces electrical power 361 that is used throughout the carbon extraction plant and the main plant.
- the heat recovery steam generator 304 is used to produce steam which is delivered to a steam bank for distribution.
- An electric motor 314 is used to drive a compressor 315 which compresses the CO 2 338 from the CO 2 absorption apparatus 310 to typically 1,000 psi so that it can be sequestered or sold.
- the CO 2 absorption apparatus 310 utilizes any of several well-known processes are used to separate the CO 2 and H 2 332 .
- Flue gases produced by the various combustion processes may also be used in ways to extract additional energy.
- the flue gas 342 from the combustion turbine is augmented by mixed gas fuel and used in a duct burner to provide heat for the steam methane reformer reactor 301 .
- the flue gas from the steam methane reformer reactor 301 is augmented by mixed gas fuel and used in a duct burner to provide energy to power the HRSG 304 .
- the de-energized flue gas 349 from the HGRS 304 is vented to the atmosphere.
- Water taken from the output of the tube evaporator (item 210 in FIG. 2 ) shown in FIG. 2 is input to a water storage tank where it is then passed through the water-gas shift reactor to be heated via heat exchanger by the exothermic reaction that occurs in the water-gas shift reactor.
- This heated water is input to the HRSG to be turned into steam.
- the steam produced in the HRSG is delivered to a steam bank for distribution to the steam methane reformer reactor; the water-gas shift reactor; and the CO 2 absorption apparatus.
- a substantial portion of the steam in the steam bank is returned to the high pressure steam separator (item 213 in FIG. 2 ) in the main plant shown in FIG. 2 .
- FIG. 4 is a partial schematic of FIG. 3 highlighting fuel and other gas pathways. This is the same as the diagram of FIG. 3 except the water and steam pathways are not shown so that the other pathways can be seen more clearly.
- FIG. 5 is a partial schematic of Figure highlighting water and steam pathways. This is the same as the diagram of FIG. 3 except only the water and steam pathways are shown so that they can be seen more clearly.
- FIG. 6 is a schematic of a pre-combustion CO 2 capture process integrated into a steam methane reforming and water-gas shift process.
- This is a pre-combustion CO 2 capture method integrated into the steam methane reforming and water-gas shift process in which natural gas is converted to CO 2 and H 2 .
- An alkali and/or an alkaline earth metal oxide, which is preferably a mixture of magnesium oxide and calcium oxide, from a first separation hopper is added to the CO 2 and H 2 and sent through a fluid bed reactor where the mixture is converted to gas stream of H 2 carrying alkali and/or an alkaline earth metal (e.g. magnesium and calcium) carbonates.
- an alkali and/or an alkaline earth metal oxide e.g. magnesium and calcium
- alkali and/or an alkaline earth metal oxides react with carbon dioxide to form alkali and/or an alkaline earth metal carbonates.
- the carbonates are added to a clean CO 2 stream (which is preferably substantially free of molecular hydrogen and even more preferably includes no more than about 15 mole % molecular hydrogen) and sent through a heat exchanger in the steam methane reformer where the alkali and/or an alkaline earth metal carbonates are calcined into alkali and/or an alkaline earth metal oxides. These are returned to the first separation hopper, where preferably most, and even more preferably at least about 85% of the CO 2 is removed and sent to a cool down apparatus. A portion of the cooled CO2 is sent to a compressor for subsequent EOR operations or for sale or for sequestering. The remainder of the CO 2 is recycled through the system where it is added to the alkali and/or an alkaline earth metal carbonates to repeat the CO 2 capture cycle.
- a clean CO 2 stream which is preferably substantially free of molecular hydrogen and even more preferably includes no more than about 15 mole % molecular hydrogen
- Utility-grade natural gas 621 is input into a steam methane reformer 601 which produces primarily carbon monoxide (CO) and hydrogen (H 2 ). This is an endothermic reaction which is operated at temperatures in the approximate range of about 850° C. to 1,100° C.
- the carbon monoxide and hydrogen gases are sent to a water-gas shift reactor 602 where preferably at least most, and even more preferably at least about 85% of the CO is converted to carbon dioxide (CO 2 ) by an exothermic reaction forming an output stream of carbon dioxide and hydrogen.
- a mixture of dry magnesium oxide (MgO) and calcium oxide (CaO) is added to this gas stream and is processed through a fluid bed reactor 607 so that most of the carbon dioxide is reacted to form magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 ).
- MgCO 3 magnesium carbonate
- CaCO 3 calcium carbonate
- the combination of magnesium carbonate and calcium carbonate allows the capture process to occur in minutes.
- the proportions of magnesium carbonate and calcium carbonate are typically those found in dolomite.
- the stream of magnesium carbonate, calcium carbonate and hydrogen is transported, with the hydrogen now acting as the carrier fluid, and input into a separation hopper 608 where at least most of the molecular hydrogen 623 is removed and the solid magnesium carbonate and calcium carbonate are stored.
- magnesium carbonate and calcium carbonate 626 are added to the recovered magnesium carbonate and calcium carbonate to allow the mixture to be recycled with full potency as described in the paper “SEM Analysis Application to Study CO 2 Capture by Means of Dolomite”, Katia Gallucci, Gustavo Paolini, Luca Di Felice, Claire Courson, Pier Ugo Foscolo and Alain Kiennemann published in the Open-Access Journal for the Basic Principles of Diffusion Theory, Experiment and Application, 2007.
- Their experimental studies show that calcined dolomite is a good sorbent of CO 2 with CaO re-carbonating at a temperature of about 800° C. It is also noted that it is possible to calcine dolomite at this same approximate temperature with adequate gas flow.
- the amount of conversion of CaO from CaCO 3 and MgO from MgCO 3 decreases with the number of calcination/re-carbonation cycles as the dolomite degrades.
- This process ultimately produces clean CO 2 .
- Some of this is diverted and compressed in compressor 606 in preparation for sequestration or use in EOR operations 622 .
- the remainder is added via path 623 to a stream of magnesium carbonate and calcium carbonate from separation hopper 608 to act as a carrier fluid.
- This stream is then input into a separate heat exchanger that forms a part of the steam methane reformer 601 where the magnesium carbonate and calcium carbonate are calcined to magnesium oxide and calcium oxide by the heat generated in steam methane reformer 601 . Additional carbon dioxide is generated during this process.
- the stream of carbon dioxide, magnesium carbonate and calcium carbonate is input into a second separation hopper 603 where the CO 2 is separated and sent to a CO 2 cool down apparatus 604 prior to compressing and sequestering.
- this carbon dioxide can also be sold as a product or used in EOR operations.
- the advantage of this process is that the magnesium oxide and calcium oxide act as a sorbent to bind carbon dioxide to form magnesium carbonate and calcium carbonate.
- the magnesium carbonate and calcium carbonate are then reduced by heat to form magnesium oxide, calcium oxide and carbon dioxide which can readily be captured.
- Some of the carbon dioxide is sequestered and some is used to form the gas stream that entrains and carries the magnesium oxide and calcium oxide through the fluid bed reactor and also entrains and carries the magnesium carbonate and calcium carbonate through the heat exchanger in the steam methane reformer. This process is possible because the temperature for steam reforming and for calcination are approximately the same and so can be carried out in a common apparatus.
- FIG. 7 is schematic of the present invention showing the principal elements of an innovative portion of an integrated SAGD operation (the carbon extraction plant) with the pre-combustion CO 2 capture process of FIG. 6 .
- FIG. 7 is similar to FIG. 3 , except the CO 2 absorption facility is replaced by the pre-combustion CO 2 capture process of FIG. 6 .
- the pre-combustion capture system is integrated in with the steam methane reformer reactor.
- natural gas 731 enters the carbon extraction plant and a first portion is reformed by the steam methane reformer reactor 701 and water-gas shift reactor 702 to produce carbon dioxide and molecular hydrogen 732 .
- the carbon dioxide is captured using the method disclosed in FIG. 6 and then compressed to 1,000 psi and stored for further use (for example, for sale, for EOR or for sequestering).
- Some of the molecular hydrogen 735 is diverted and mixed with a second portion of the natural gas brought into the carbon extraction plant to produce a mixed gas of about 60% natural gas and about 40% hydrogen. This mixed gas is used to power a combustion turbine 706 which generates electrical power output.
- this mixed gas is also used to power: the steam methane reformer reactor 701 ; the fluid bed reactor 710 ; and a heat recovery steam generator (“HRSG”) 704 which produces steam from water input which, in turn, comes from the output of the tube evaporator shown in FIG. 2 .
- HRSG heat recovery steam generator
- This steam from the HRSG is used in the steam methane reformer reactor 701 and water-gas shift reactor 702 .
- the steam not utilized in the reforming/water-gas shift process is returned to the high pressure steam separator shown in FIG. 2 .
- An electrical motor is used to drive power turbine 714 which, in turn, drives a compressor 715 which compresses the carbon dioxide 737 to about 1,000 psi.
- the remainder of the hydrogen produced 736 is sent out of the carbon extraction plant and mixed with the natural gas that by-passed the carbon extraction plant to form a second mixed gas fuel (typically about 60% natural gas and about 40% hydrogen) that is used in the burners of the steam drum generators shown in FIG. 2 .
- a second mixed gas fuel typically about 60% natural gas and about 40% hydrogen
- Natural gas 731 used as the primary fuel to power the operation, is input as shown. Some of the natural gas 731 is mixed with molecular hydrogen (“H 2 ”) to form a mixed gas fuel. The remainder of the natural gas 731 is sent through a heat exchanger 706 to be heated by the output gases from the water-gas shift reactor 702 and then to pick up more heat from the output gases from the steam methane reformer reactor 701 and is then fed into the steam methane reformer reactor 701 to be combined with steam and reformed into syn gas.
- Syn gas is carbon monoxide (“CO”) and hydrogen molecular (“H 2 ”) with some carbon dioxide (“CO 2 ”).
- the output of the steam methane reformer reactor 701 is sent to the water-gas shift reactor 702 where it is combined with steam to form primarily carbon dioxide (“CO 2 ”) and molecular hydrogen (“H 2 ”) 732 .
- a portion of utility-grade natural gas 731 is input into a steam methane reformer 701 which produces primarily carbon monoxide (CO) and molecular hydrogen (H 2 ).
- the carbon monoxide and molecular hydrogen gases are sent to a water-gas shift reactor 702 where most of the CO is converted to CO 2 by an exothermic reaction forming an output stream of carbon dioxide and molecular hydrogen.
- a mixture of dry magnesium oxide (MgO) and calcium oxide (CaO) is added to this gas stream and is processed through a fluid bed reactor 710 so that most of the carbon dioxide is reacted to form magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 ).
- the stream of magnesium carbonate, calcium carbonate and molecular hydrogen is transported, with the molecular hydrogen now acting as the carrier fluid, and input into a separation hopper 712 where the molecular hydrogen is removed and the solid magnesium carbonate and calcium carbonate are stored. Some additional magnesium carbonate and calcium carbonate are added to the recovered magnesium carbonate and calcium carbonate to allow the mixture to be recycled with full potency.
- This process ultimately produces clean CO 2 .
- Some of this is diverted and compressed in compressor 715 in preparation for sequestration or use in EOR operations 737 .
- the remainder is added via path 723 to a stream of magnesium carbonate and calcium carbonate from separation hopper 708 to act as a carrier fluid.
- This stream is then input into a separate heat exchanger that forms a part of the steam methane reformer 701 where the magnesium carbonate and calcium carbonate are calcined to magnesium oxide and calcium oxide by the heat generated in steam methane reformer 701 . Additional carbon dioxide is generated during this process.
- the stream of carbon dioxide, magnesium carbonate and calcium carbonate is input into a second separation hopper 708 where the CO 2 is separated and sent to a CO 2 cool down apparatus 709 prior to compressing and sequestering.
- this carbon dioxide can also be sold as a product or used in EOR operations.
- Flue gases produced by the various combustion processes are also used in ways to extract addition energy.
- the flue gas from the combustion turbine is augmented by mixed gas fuel and used in a duct burner to provide heat for the steam methane reformer reactor.
- the flue gas from the steam methane reformer reactor is augmented by mixed gas fuel and used in a duct burner to provide the power to drive the second turbine which operates the compressor.
- the flue gas from the second turbine is augmented by mixed gas fuel and used in a duct burner to provide energy to power the HRSG.
- the flue gas from the HGRS is vented to the atmosphere.
- the flue gases from the heat recovery steam generator may be treated by a post combustion carbon dioxide capture process.
- Water taken from the output of the evaporator shown in FIG. 2 is input to a water storage tank where it is then passed through the water-gas shift reactor to be heated via heat exchange by the exothermic reaction that occurs in the water-gas shift reactor.
- This heated water is input to the HRSG to be turned into steam.
- the steam produced in the HRSG is delivered to a steam bank for distribution to the steam methane reformer reactor; and the water-gas shift reactor. A substantial portion of the steam in the steam bank is returned to the high pressure steam separator in the main plant shown in FIG. 2 .
- the carbon extraction plant could be used in conjunction with an electrical power generating plant to form an energy efficient facility run on natural gas where a portion of the natural gas is reformed to eliminate some fossil carbon.
- the present invention in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, sub-combinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure.
- the present invention in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, for example for improving performance, achieving ease and/or reducing cost of implementation.
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Abstract
The present invention is directed to the recovery of hydrocarbons wherein a portion of carbon is removed from the product by a combination of reforming and water-gas shift. The resulting carbon dioxide is removed by known techniques to provide a fuel having reduced levels of carbon.
Description
- The present application claims the benefits, under 35 U.S.C. §119(e), of U.S. Provisional Application Ser. No. 61/078,690 filed Jul. 7, 2008, entitled “Carbon Removal from an Integrated Thermal Recovery Process” and U.S. Provisional Application Ser. No. 61/115,822 filed Nov. 18, 2008, entitled “Carbon Removal from an Integrated Thermal Recovery Process” to Gil and Squires, both of which are incorporated herein by these references.
- The present invention relates generally to a method and means of removing a portion of carbon from natural gas used to provide steam and electrical power for a large hydrocarbon thermal recovery plant.
- There are many hydrocarbon producing regions around the world. These regions may produce hydrocarbons by conventional means or, as production from conventional sources declines, by non-conventional means. For example, conventional means include drilling wells and pumping crude oil or natural gas to the surface. Non-conventional means include recovering bitumen and heavy oil by, for example, thermal stimulation or mining. Producers, especially of some of the non-conventional means which generate significant additional fossil carbon dioxide during recovery and upgrading, are becoming more and more regulated as the link between carbon dioxide emissions and global warming becomes understood.
- A prime example of such producers are Steam Assisted Gravity Drain (“SAGD”) and Cyclical Steam Stimulation (“CSS”) operators in the Western Canadian Sedimentary Basin which contains immense reserves of unconventional hydrocarbons, principally in the form of bitumen and heavy oil.
- In a conventional SAGD operation, for example, bitumen is recovered, and the bitumen is separated from the recovered water. The water is treated so that it can be used to produce steam in boilers. Diluents are added to the bitumen so that it can be transported by pipeline. Steam is produced primarily by using a fossil fuel energy source such as natural gas, coal, a fuel derived from bitumen and the like. These operations require substantial amounts of energy, much of which is wasted. These operations also generate large amounts of carbon dioxide when producing steam and electrical power and this carbon dioxide is usually released into the atmosphere.
- Producing regions such as the Western Canadian Sedimentary Basin are increasingly coming under regulatory pressures to reduce emissions of fossil carbon dioxide, wherein each producer is given the choice of reducing its carbon dioxide emissions, trading for carbon credits or paying a carbon tax. For example, a producer may choose to reduce their fossil carbon dioxide emissions by installing on-site carbon capture and sequestration facilities. In the case of many producers of unconventional hydrocarbons, trading for carbon credits or paying a carbon tax is a less costly and, in the short term, a less risky course of action.
- There remains, therefore, a need for an economical method and means of managing the reduction of carbon dioxide emissions from such operations.
- These and other needs are addressed by the present invention. The various embodiments and configurations of the present invention are directed generally to a process of removing a portion of carbon from natural gas used to generate steam and electrical power e power for a for a hydrocarbon thermal recovery plant, such as for example a SAGD or CSS plant.
- In a first embodiment, a process comprising the steps: (a) receiving a gas stream comprising primarily methane; (b) removing a first portion of the gas stream from a second portion of the gas stream; (c) converting the first portion of the gas stream to produce a reformed and water-gas shifted gas comprising primarily carbon dioxide and molecular hydrogen; (d) removing, from the reformed and water-gas shifted gas, at least most of the carbon dioxide to form a product gas; and (e) thereafter combining the product gas with the second portion of the gas stream to form a mixed gas, whereby a carbon content of the mixed gas is reduced relative to the received gas stream.
- In second embodiment, a system comprising: an input to receive a gas stream comprising primarily methane; a gas separator to remove a first portion of the gas stream from a second portion of the gas stream; a steam methane reformer reactor to convert the first portion of the gas stream to a reformed gas comprising primarily molecular hydrogen and carbon monoxide; a water-gas shift reactor to convert the reformed gas into a reformed and water-gas shifted gas comprising primarily carbon dioxide and molecular hydrogen; a carbon separator to remove, from the reformed and water-gas shifted gas, at least most of the carbon dioxide to form a product gas; and a gas combiner to combine the product gas with the second portion of the gas stream to form a mixed gas, whereby a carbon content of the mixed gas is reduced relative to the received gas stream.
- In other embodiments, a method/system is/are provided that perform the following steps/operations: (a) forming, from an input gas stream comprising primarily methane, an intermediate gas stream comprising primarily gas-phase molecular hydrogen and carbon oxide; (b) contacting the intermediate gas stream with an alkali and/or alkaline earth metal oxide to form a second intermediate gas stream comprising molecular hydrogen and carbonates; (c) removing at least most of the molecular hydrogen from the second intermediate gas stream to form a product gas stream comprising primarily molecular hydrogen and a third intermediate gas stream comprising at least most of the carbonates; (d) converting, using heat from the forming step (a), at least most of the carbonates in the third intermediate gas stream to gas-phase carbon oxide and alkali and/or alkaline earth metal oxide; (e) removing at least most of the gas-phase carbon oxide from the alkali and/or alkaline earth metal oxide; and (f) recycling the separated alkali and/or alkaline earth metal oxide to step (b).
- In one configuration, the product gas comprises no more than about 25% of the carbon present in the input gas stream.
- The various embodiments can have a number of advantages. By way of example, the embodiments can reduce significantly fossil carbon emissions from fossil fuels. The embodiments can convert fossil carbon into carbon dioxide for sequestration. The resulting molecular hydrogen is itself a fuel. The embodiments can significantly reduce, relative to conventional processes, energy waste. By using energy more efficiently, heavy oil deposits may be exploited more inexpensively.
- The following definitions are used herein:
- Calcination (also referred to as calcining) is a thermal treatment process applied to ores and other solid materials in order to bring about a thermal decomposition, phase transition, or removal of a volatile fraction. The calcination process normally takes place at temperatures below the melting point of the product materials. Calcination takes place in the absence of air. The process of calcination derives its name from its most common application, the decomposition of calcium carbonate (limestone) to calcium oxide (lime).
- The product of calcination is usually referred to in general as “calcine,” regardless of the actual minerals undergoing thermal treatment
- A carbon sequestration facility is a facility in which carbon dioxide can be controlled and sequestered in a repository such as for example a mature or depleted oil and gas reservoir, an unmineable coal seam, a deep saline formation, a basalt formation, a shale formation, or an excavated tunnel or cavern.
- Dilbit is short for diluted bitumen. Typically, dilbit is about 65% bitumen diluted with about 35% naphtha. The naphtha is added to make a fluid that can be transported by pipeline by reducing the viscosity of the bitumen/naphtha mixture. The dilbit can be transported by pipeline to a refinery. The naphtha diluent can be taken out as a straight run naphtha/gasoline and reused as diluent. Or it is processed to products in the refinery. The dilbit has a lot of light hydrocarbons from the diluent and a lot of heavy hydrocarbons from the bitumen. So it is a challenge to process directly in a normal refinery. Dilbit can only be a small part of a normal refinery's total crude slate. In addition to naphtha, condensate can also be used as diluent.
- A duct burner as used herein is any industrial combustor or burner that is operated at close to ambient pressure.
- EOR stands for Enhanced Oil Recovery
- HRSG stands for Heat Recovery Steam Generator. A heat recovery steam generator or HRSG is a heat exchange apparatus that recovers heat from a hot gas stream to produce steam. The hot gas stream can be provided, for example, by the hot exhaust from a gas turbine.
- A hydrocarbon transport means as used herein includes any means of bulk hydrocarbon transport including but not limited to a pipeline, a train of tank cars or gondolas, a ship, a barge or a truck convoy.
- A mobilized hydrocarbon is a hydrocarbon that has been made flowable by some means. For example, some heavy oils and bitumen may be mobilized by heating them or mixing them with a diluent to reduce their viscosities and allow them to flow under the prevailing drive pressure. Most liquid hydrocarbons may be mobilized by increasing the drive pressure on them, for example by water or gas floods, so that they can overcome interfacial and/or surface tensions and begin to flow.
- Natural gas refers to a hydrocarbon gas including low molecular weight hydrocarbons, primarily methane. The low molecular weight hydrocarbons commonly include, in addition to methane, ethane, propane, and butane. A typical natural gas-containing product contains from about 50 to about 98 mole percent methane, from about 1 to about 15 mole percent ethane, and up to about 5 mole percent propane and butane. The product may contain various sulfur, nitrogen and carbon dioxide compounds as contaminants.
- Pipeline quality natural gas is specified for example by the American Gas Association and Canadian Gas Association. Typically, there are limits on sulphur, carbon dioxide, water and other constituents of natural gas obtained from nature to comply with pipeline specifications.
- Primary production or recovery is the first stage of hydrocarbon production, in which natural reservoir energy, such as gas-drive, water-drive or gravity drainage, displaces hydrocarbons from the reservoir, into the wellbore and up to surface. Production using an artificial lift system, such as a rod pump, an electrical submersible pump or a gas-lift installation is considered primary recovery. Secondary production or recovery methods frequently involve an artificial-lift system and/or reservoir injection for pressure maintenance. The purpose of secondary recovery is to maintain reservoir pressure and to displace hydrocarbons toward the wellbore. Tertiary production or recovery is the third stage of hydrocarbon production during which sophisticated techniques that alter the original properties of the oil are used. Enhanced Oil Recovery can begin after a secondary recovery process or at any time during the productive life of an oil reservoir. Its purpose is not only to restore formation pressure, but also to improve oil displacement or fluid flow in the reservoir. The three major types of enhanced oil recovery operations are chemical flooding, miscible displacement and thermal recovery.
- A producer is a any producer of natural gas, oil, heavy oil, bitumen, peat or coal from a hydrocarbon reservoir.
- Reforming means fossil fuel reforming which is a method of producing useful products, such as hydrogen or ethylene from fossil fuels. Fossil fuel reforming is done through a fossil fuel processor or reformer. At present, the most common fossil fuel processor is a steam reformer. This conversion is possible as hydrocarbons contain much hydrogen. The most commonly used fossil fuels for reforming today are methanol and natural gas, yet it is possible to reform other fuels such as propane, gasoline, autogas, diesel fuel, methanol and ethanol. During the conversion, the leftover carbon dioxide is typically released into the atmosphere. On an industrial scale, reforming is the dominant method for producing hydrogen. The basic chemical reaction for reforming is:
-
CnHm +nH2O→nCO+(m/2+n)H2 - This reaction is endothermic. The produced carbon monoxide can combine with more steam to produce further hydrogen via the water gas shift reaction.
- Synbit is a blend of bitumen and synthetic crude. Synthetic crude is a crude oil product produced, for example, by the upgrading and refining of bitumen or heavy oil. Typically, synbit is about 50% bitumen diluted with about 50% synthetic crude.
- SMR stands for Steam Methane Reformer.
- Syngas (from synthesis gas) is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen. Examples of production methods include steam reforming of natural gas or liquid hydrocarbons to produce hydrogen, the gasification of coal and in some types of waste-to-energy gasification facilities. The name comes from their use as intermediates in creating synthetic natural gas and for producing ammonia or methanol. Syngas is also used as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via Fischer-Tropsch synthesis and previously the Mobil methanol to gasoline process. Syngas consists primarily of hydrogen, carbon monoxide, and very often some carbon dioxide, and has less than half the energy density of natural gas. Syngas is combustible and often used as a fuel source or as an intermediate for the production of other chemicals.
- Upgrading (including partial upgrading) as used herein means removing carbon atoms from a hydrocarbon fuel, replacing the removed carbon atoms with hydrogen atoms to produce an upgraded fuel and then combining the carbon atoms with oxygen atoms to form carbon dioxide.
- The water-gas shift reaction is a chemical reaction in which carbon monoxide reacts with water to form carbon dioxide and hydrogen:
-
CO+H2O→CO2+H2 - The water-gas shift reaction is often used in conjunction with steam reforming of methane or other hydrocarbons. The water-gas shift reaction is slightly exothermic, yielding 42 kJ per mole. The process is often used in two stages, stage one a high temperature shift at 350° C. and stage two, a low temperature shift at 190 to 210° C.
- It is to be understood that a reference to diluent herein is intended to include solvents.
- It is to be also understood that a reference to oil herein is intended to include low API hydrocarbons such as bitumen (API less than ˜10°) and heavy crude oils (API from ˜10° to ˜20°) as well as higher API hydrocarbons such as medium crude oils (API from ˜20° to ˜35°) and light crude oils (API higher than ˜35°). A reference to bitumen is also taken to mean a reference to low API heavy oils.
- “At least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
-
FIG. 1 is a schematic showing the principal elements of a typical prior art SAGD operation using natural gas for power. -
FIG. 2 is schematic of the present invention showing the principal elements of an integrated SAGD operation using natural gas for power. -
FIG. 3 is a schematic of the present invention showing the principal elements of the innovative portion of an integrated SAGD operation ofFIG. 2 . -
FIG. 4 is a partial schematic ofFIG. 3 highlighting fuel and other gas pathways. -
FIG. 5 is a partial schematic of Figure highlighting water and steam pathways. -
FIG. 6 is a schematic of a pre-combustion CO2 capture process. -
FIG. 7 is schematic of the present invention showing the principal elements of the innovative portion of an integrated SAGD operation with the pre-combustion CO2 capture process ofFIG. 6 . - In various embodiments, natural gas is used as the primary energy source but a first portion of the natural gas is reformed to produce carbon dioxide and hydrogen in a carbon extraction plant integrated into a main bitumen process plant. The carbon dioxide is liquified and can be sequestered, used for EOR operations, sold or otherwise controlled such that it is not released into the atmosphere. The hydrogen is mixed with a second portion of the natural gas to produce a high energy fuel for operating other apparatuses in the plant. This removal of a portion of carbon from the emissions requires some additional energy but the plant is configured in such a way as to utilize as much waste heat as possible so that the overall plant processes more bitumen and releases less carbon dioxide for about the same energy consumption as a conventional SAGD operation. As a result the plant operator may be eligible for a carbon credit or at least a reduced carbon tax.
- In one configuration carbon dioxide is removed pre-combustion by well known processes such as for example the Selexol process. In another configuration, carbon dioxide is removed pre-combustion by a fluidized bed reactor approach and carbon dioxide is removed from the sorbent by heat generated in the steam methane reformer reactor.
-
FIG. 1 is a schematic showing the principal elements of a typical prior art SAGD operation using natural gas for power. In this example, 30,000 barrels per day (“bpd”) of bitumen are processed using approximately 34 million standard cubic feet per day of natural gas as fuel. This translates to 1,133 standard cubic feet per day of natural gas burned to process a barrel of bitumen. The eventual product of this plant is a 19° to 20° API dilbit. Often bitumen recovered from a SAGD operation is shipped to a refinery for upgrading. If shipment is made by pipeline, a diluent must be added to the bitumen to allow the blend to flow. In a typical SAGD operation, recovered bitumen is partially upgraded to an approximately 20° API product which can then be transported by pipeline to a refinery. - As shown in
FIG. 1 , raw bitumen-water feedstock from awell pad facility 102 is fed into a bitumen-water separation sequence comprising a Free Water Knock-Out (“FWKO”)unit 103.Diluent 106 is added to the raw bitumen-water feedstock to form a pumpable mixture prior to entering theFWKO unit 103. TheFWKO unit 103 separates most of the diluent-bitumen mixture (“dilbit”). This dilbit mixture is then sent to anoil treatment unit 104 which separates the remaining water from the dilbit.Additional diluent 107 is added to the dilbit product which is then sent to aproduct storage tank 105, where it remains ready, for example, for transport bypipeline 108 to an upgrader. - The water from the
oil treatment unit 104 is sent to ade-oiling unit 110 for final cleaning of remaining oil residue. The oil residue from thede-oiling unit 110 is returned to the feedstock of theFWKO unit 103. Make-upwater 116 from a water well source is added to the de-oiled water and then fed to a series of water treatment apparatuses which purify the water in preparation for making steam. The water treatment apparatuses are typically comprised ofwater softener units 111, walnut filter unit 114 and anion exchange unit 115. The treated water is fed to steamgenerators 121 which are used to produce primarily hot dry steam which is sent to a high pressuresteam separator unit 122.Natural gas 123 is used to power thesteam generators 121. These steam generators may be large single pass boilers or they may be multi-pass drum steam generators. In the 30,000 bpd example, about 2,700 tons per day of CO2 is released 125 into the atmosphere by thedrum steam generators 121 which is about 0.09 tons CO2 released per barrel of bitumen processed. - The high pressure
steam separator unit 122 compresses the steam from thesteam generators 121 and delivers the hot, high-pressure, high-quality steam to thewell pads 102 for injection into thebitumen reservoir 101 where it is used to continue the bitumen mobilization and recovery process. Condensate (˜1 to 2% of the steam) from the high pressuresteam separator unit 122 is handled by ablowdown apparatus 124 and sent to a water disposal well 126. -
FIG. 2 is schematic of the present invention showing the principal elements of an integrated SAGD operation using natural gas for power.Natural gas fuel 221 is brought into the facility and a substantial fraction of the natural gas is diverted by a gas separator and reformed and water-gas shifted in a carbon extraction plant to eliminate carbon in the form of captured carbon dioxide (“CO2”). As will be discussed inFIG. 3 , this is done while also generating electrical energy and steam. Therefore, an innovation is the addition of a carbon extraction plant that modifies a portion of the natural gas fuel input to the main plant. The carbon extraction plant delivers clean CO2, molecular hydrogen and electrical power. The molecular hydrogen is then mixed by a gas combiner with portion of natural gas not sent to the carbon extraction plant to form a mixed gas fuel which is then used to power steam generators and other apparatuses in the main plant. In a typical application, at least about 20% of the methane by volume, more typically about 40% of the methane by volume, and as high as about 60% of the methane by volume of the natural gas is converted into molecular hydrogen. Relative to conventional processes in which natural gas is combusted, this use of mixed fuel commonly reduces fossil carbon emissions by at least about 20% and as high as about 60%. - In the example of
FIG. 2 , 40,000 barrels per day (“bpd”) of bitumen are processed using approximately 42 million standard cubic feet per day of natural gas asfuel 221. This translates to 1,050 standard cubic feet per barrel of bitumen or slightly more efficient than the prior art plant described inFIG. 1 . However, only 26 million standard cubic feet per day of natural gas are burned since 16 million standard cubic feet per day of natural gas are reformed and water-gas shifted to remove carbon. Thus, in the present invention, only 650 standard cubic feet of natural gas is burned to process a barrel of bitumen. The remaining energy required to operate the plant is obtained from molecular hydrogen (“H2”) generated by the reforming and water-gas shift processes. The reforming and water-gas shift processes also generate 31 million standard cubic feet per day of CO2 which is captured, purified and compressed to 1,000 psi. The bitumen product is a 19° to 20° API dilbit which is the same as that of the prior art plant described inFIG. 1 . - The raw feedstock for the process of the present invention is bitumen or heavy oil recovered by a mining or in-situ operation. An example of a mining operation would be a hydraulic mining operation which produces an oil sand slurry. An example of hydraulic mining conducted from an underground workspace is disclosed in U.S. Provisional Patent Application No. 60/867,010 entitled “Recovery of Bitumen by Hydraulic Excavation” to Brock, Squires, Watson and filed Nov. 22, 2006 which is incorporated herein by this reference. The bitumen, water and sand from a hydraulic mining operation can be separated, for example, by hydrocyclone methods. An example of this method of separation is disclosed in U.S. Pat. No. 7,128,375 issued Oct. 31, 2006, entitled “A Method and Means for Recovering Hydrocarbons from Oil Sands by Underground Mining” to Watson also which is incorporated herein by this reference.
- An example of an in-situ recovery operation is a Steam Assisted Gravity Drain (“SAGD”) operation which produces a product stream of water, hot bitumen and gas. SAGD operations can be carried out from a surface facility or from an underground workspace. An example of this latter approach is disclosed in U.S. patent application Ser. No. 11/441,929 entitled “Method for Underground Recovery of Hydrocarbons” to Brock, Kobler and Watson, filed May 26, 2006.
- The bitumen recovered from a thermal recovery operation such as SAGD or Cyclical Steam Stimulation (“CSS”) contains a large amount of water. A small fraction is connate water but most of the water is produced as condensate from the steam used to heat and mobilize the bitumen. As shown in the example of
FIG. 2 , aSAGD steam chamber 200 is the reservoir or source of bitumen, condensed water along with dissolved and free gases such as CH4, CO2, H2S and other trace gases. The source material is recovered from thesteam chamber 200 by producer wells such as used, for example, in SAGD or CSS, or by non-thermal processes such as VAPEX or by a combination of these processes that can cause the bitumen to be mobilized and recovered. The produced source material is then sent to anunderground location 201 for storage and processing or for storage, pumping to the surface and processing. Thus, the process of the present invention may be carried out on the surface, underground or portions of the process may be carried out underground. While the producer well-heads are assumed to be underground for purposes of the present illustration, the well heads may be located on the surface. - One of the products of the process of the present invention is hot, dry, pressurized steam which may be returned to the underground location and finally to the
reservoir 200 for ongoing steaming (SAGD or CSS) operations. Other products of the process of the present invention, such as for example, CO2, NOx and SO2, may also be captured and returned to the underground location and finally to thereservoir 200 or other geologic repository for sequestration. - The raw bitumen-water feedstock from
underground storage 201 is fed into a bitumen-water separation sequence comprising a Free Water Knock-Out (“FWKO”)unit 203.Diluent 202 is added to the raw bitumen-water feedstock to form a pumpable mixture prior to entering theFWKO unit 203. - The de-oiled bitumen-diluent mixture from the
FWKO unit 203 is fed to anoil treating unit 204 where at least most of the residual water is removed and added to the input of thewater de-oiling unit 208. The treated hydrocarbon mixture, typically, dilbit is sent to aproduct storage tank 205.Additional diluent 206 is added to the dilbit product so that it can be transported bypipeline 207 to an upgrader. - In a typical 40,000 barrel per day (“bpd”) bitumen recovery operation, typically about 55,000 bpd of 19° to 20° API dilbit is produced, the exact amount of dilbit produced being a function of the API grade of the recovered bitumen.
- The
FWKO unit 203 separates most of the water which is then sent to ade-oiling unit 208 for final cleaning of remaining oil residue. The oil residue from thede-oiling unit 208 is returned to the feedstock of theFWKO unit 203. Make-up water from awater well source 209, for example, is added to the de-oiled water and then fed to atube evaporator 210 which distills the water in preparation for making steam. Some water is condensed in thetube evaporator 210 and is processed by ablowdown treatment apparatus 215 and then returned to the ground via a water disposal well 216. It is understood that reference to a tube evaporator may mean a rising tube evaporator or a falling tube evaporator since both accomplish the same function in process of the present invention. - In a typical 40,000 barrel per day bitumen recovery operation, from about 80,000 to about 150,000 bpd of water may be recovered. Most of this is condensate when a thermal process such as SAGD is used. Typically there is on the order of about 100 to 125 kg of connate water and on the order of about 200 to 300 kilograms bitumen recovered for every cubic meter of in-situ deposit mobilized. In a typical 40,000 bpd SAGD bitumen recovery operation, an amount of make-up water from the
water well source 209 is added to the de-oiled water prior to being fed to thetube evaporator 210. The amount of make-up water is in the range of about 5% to about 15% of the amount of water recovered from the SAGD operation. - The distilled water from the
tube evaporator 210 is fed to thesteam drum generators 212 which are used to produce primarily hot dry steam which is sent to a high pressuresteam separator unit 213. A mixture of molecular hydrogen and methane (called a mixed gas) are used to power thesteam drum generators 212 as described below. The primary function of thesteam drum generators 212 is to produce high quality steam which is transferred to a high pressuresteam separator unit 224. - The high pressure
steam separator unit 213 compresses the steam from thesteam drum generators 212 and delivers the hot, high-pressure, high-quality steam to theunderground facility 200 for subsequent use in maintaining temperature and pressure conditions in steam chamber. Water condensate from the high pressuresteam separator unit 213 is returned to thetube evaporator 210. - As discussed above,
natural gas fuel 221 is brought into the facility and a substantial fraction of the natural gas is diverted and reformed and water-gas shifted to eliminate carbon in the from of captured carbon dioxide (“CO2”) in acarbon extraction plant 214. A portion of inputnatural gas 221 is diverted through thecarbon extraction plant 214 and hydrogen 228 is output and mixed with the natural gas that by-passes thecarbon extraction plant 214, to form a mixed gas which is typically about 40% molecular hydrogen and about 60% natural gas by volume. The amount of the natural gas fuel diverted through theplant 214 depends on the application and local carbon emission regulations and the mixed gas may vary in composition from about 20% to about 60% molecular hydrogen by volume, corresponding to about 80% to about 40% natural gas by volume. - The overall steam reforming and water-gas shift reaction is:
-
CH4+2H2O→CO2+4H2 - Thus for each methane molecule input, four molecules of hydrogen and one molecule of carbon dioxide are created. The carbon dioxide is captured and available to be sequestered.
- Most of the electrical power for the entire operation is generated in the
carbon extraction plant 214. Thecarbon extraction plant 214 is also referred to as a Power-SMR-Steam unit (SMR stands for Steam Methane Reformer). - The first step of the SMR process involves methane reacting with steam at 850° C. or above to produce a synthesis gas (syngas), a mixture primarily made up of molecular hydrogen (H2) and carbon monoxide (CO). In the reforming step, typically about 90% to about 95% of the methane is converted to carbon monoxide and molecular hydrogen. In the second step, known as a water gas shift (WGS) reaction, the carbon monoxide produced in the first reaction is reacted with steam over a catalyst to form molecular hydrogen and carbon dioxide (CO2). This process can be accomplished in a high temperature shift reactor at about 350° C. or in a low temperature shift reactor at about 190° C. to about 210° C. In the water shift step, more than about 90% of the carbon monoxide is typically converted to carbon dioxide.
- In this example, 42 MMSCFD of natural gas enters the plant and 16 million standard cubic feet per day (about 38%) is diverted to
carbon extraction plant 214. As will be discussed inFIG. 3 , thecarbon extraction plant 214 outputs over 30 million standard cubic feet per day of CO2 at 1,000 psi; 24 MW of electrical power; around 200,000 lbs per hour of steam and about 64 million standard cubic feet per day of hydrogen. - The steam is added to the high
pressure steam separator 213; the 24 MW of power is used to operate the various units in thecarbon extraction plant 214 and the main plant; theCO 2 223 is sold, used for EOR or sequestered; and the recovered hydrogen 226 is mixed with the 26 million standard cubic feet per day ofnatural gas 221 to produce a high energy gas mix that is used in the burners of thesteam drum generators 212. Thus, thecarbon extraction plant 214 removes a substantial portion of fossil carbon while using slightly less energy to process a barrel of bitumen and produce steam than the prior art plant ofFIG. 1 . - About 2,880 tons per day of CO2 is released into the atmosphere by the
drum steam generators 212 which is about 0.072 tons CO2 released per barrel of bitumen processed. - In the example of
FIG. 2 , 40,000 bpd of bitumen is processed using 42 million standard cubic feet of natural gas and releasing 2,880 tons of CO2 into the atmosphere. In the prior art plant ofFIG. 1 , 30,000 bpd of bitumen is processed using 34 million standard cubic feet of natural gas and releasing 2,700 tons of CO2 into the atmosphere. Thus the integrated plant ofFIG. 2 releases only about 80% the carbon dioxide per barrel of bitumen processed as does the prior art plant ofFIG. 1 . By increasing the portion of incoming natural gas diverted to the carbon extraction plant, the integrated plant can release as little as about 70% the carbon dioxide per barrel of bitumen processed as does the prior art plant. -
FIG. 3 is a schematic of the present invention showing a carbon extraction plant (item 214 inFIG. 2 ) which is a principal innovative system of the integrated SAGD operation described inFIG. 2 . - Natural gas is the fuel for the carbon extraction plant. The natural gas is pre-heated to a temperature commonly less than 850° C. (the temperature at which the methane molecules break apart) by two heat exchangers then used as fuel for a steam methane reformer reactor and water-gas shift reactor. In the steam methane reformer, at least most of the methane in the input natural gas stream is converted into molecular hydrogen and carbon monoxide. The output of the
steam methane reformer 301 ranges from about 25 to about 95 mole percent molecular hydrogen (H2) and from about 5 to about 75 mole percent carbon monoxide (CO). The water-gas shift process converts typically at least most and more typically about 90% to about 95% of CO to CO2. The output of these two processes is CO2 and H2 which goes to a CO2 absorption (or carbon separator) apparatus. Typically, at least about 90% and as much as about 95% of the methane is converted into carbon dioxide and molecular hydrogen by the combined processes. A portion of the CO2 is directed to an electrically powered compressor to create CO2 for sale, for EOR operations or for delivery to be sequestered. A second portion of the H2 from the CO2 absorption apparatus is purified. Some of this H2 may be removed for sale and some is mixed with a portion of natural gas in gas fuel mixer to make a mixed gas fuel. This mixed gas fuel is used to power a combustion turbine, the steam methane reformer, an HRSG facility and the CO2 absorption apparatus. Water is brought in and preheated in the water-gas shift reactor to a temperature ranging from about 50° C. to about 300° C. and then sent to the HRSG facility where steam is produced and sent to a steam bank. Some steam is sent back to the steam generators in the main plant. Some steam is sent to the steam methane reformer, some to the water-gas shift reactor and some to the CO2 absorption apparatus. Flue gases from the combustion turbine are mixed with fuel and used in a duct burner in the steam methane reformer to power the HRSG facility. - In the 40,000 bpd example of
FIG. 2 , 26 million standard cubic feet per day ofnatural gas 331 enters the carbon extraction plant and a first portion is reformed by the steammethane reformer reactor 301 and water-gas shift reactor 302 to produce carbon dioxide andhydrogen 332. The carbon dioxide is captured by one of several well-know methods and then compressed to 1,000 psi and stored for further use (for example, for sale, for EOR or for sequestering). Some of themolecular hydrogen 337 exiting the water-gas shift reactor 302 is diverted and mixed with a second portion of the natural gas brought into the carbon extraction plant to produce a mixed gas which is typically about 40% molecular hydrogen and about 60% natural gas by volume. The amount of the natural gas fuel diverted through theplant 214 depends on the application and local carbon emission regulations and the mixed gas may vary in composition from about 20% to about 60% molecular hydrogen, corresponding to about 80% to about 40% natural gas by volume. This mixed gas is used to power acombustion turbine 306 which generates, in this example, about 24 MW ofelectrical power 361. Using duct burners, for example, this mixed gas is also used to power: the steammethane reformer reactor 301; a heat recovery steam generator (“HRSG”) 304 which produces steam fromwater 352 input from the output of the tube evaporator (item 210 inFIG. 2 ) shown inFIG. 2 ; and a CO2 absorption apparatus 310. The steam from the HRSG is used in the steammethane reformer reactor 301, water-gas shift reactor 302 and CO2 absorption apparatus 310. The steam not utilized in the carbon extraction plant is returned to the high pressure steam separator (item 213 inFIG. 2 ) shown inFIG. 2 . An electrical motor is used to drive power turbine 1014 which, in turn, drives a compressor 1015 which compresses the carbon dioxide 1037 to about 1,000 psi. The remainder of the hydrogen produced 336 is sent out of the carbon extraction plant and mixed with the natural gas that by-passed the carbon extraction plant to form a second mixed gas fuel (typically about 60% natural gas and about 40% hydrogen) that is used in the burners of the steam drum generators (item 212 inFIG. 2 ) shown inFIG. 2 . -
Natural gas 331, used as the primary fuel to power the operation, is input as shown. Some of thenatural gas 331 is mixed with hydrogen (“H2”) 337 to form amixed gas fuel 341. The remainder of thenatural gas 331 is sent through aheat exchanger 306 to be heated by the output gases from the water-gas shift reactor 302 and then to pick up more heat from the output gases from the steammethane reformer reactor 301 and is then fed into the steammethane reformer reactor 301 to be combined with steam and reformed into syn gas. Syn gas is carbon monoxide (“CO”) and molecular hydrogen (“H2”) with some carbon dioxide (“CO2”). The output of the steammethane reformer reactor 301 is sent to the water-gas shift reactor 302 where it is combined with steam to form primarily carbon dioxide (“CO2”) and molecular hydrogen (“H2”) 332. In the water-shift reactor 302, typically at least about 80% and more typically at least about 90% of the carbon monoxide is converted into carbon dioxide. These gases are then sent to a CO2 absorption (or carbon separator)apparatus 310 where any of several well-known processes are used to separate the CO2 and H2. The H2 is sent to apurifier 313 where aportion 337 is then used to mix with natural gas to form a mixed gas fuel (typically about 60% natural gas and about 40% hydrogen by volume). The remainder is sent back to the main plant (FIG. 2 ) where it can also be used to form a mixed gas fuel. - In the carbon extraction plant of
FIG. 3 , the mixed gas fuel, mixed in thegas fuel mixer 319, is used to power the steammethane reformer reactor 301; acombustion turbine 306; a heat recovery steam generator (“HRSG”) 304; and a CO2 absorption apparatus 310. Thecombustion turbine 306 drives agenerator 307 which produceselectrical power 361 that is used throughout the carbon extraction plant and the main plant. The heatrecovery steam generator 304 is used to produce steam which is delivered to a steam bank for distribution. Anelectric motor 314 is used to drive acompressor 315 which compresses theCO 2 338 from the CO2 absorption apparatus 310 to typically 1,000 psi so that it can be sequestered or sold. The CO2 absorption apparatus 310 utilizes any of several well-known processes are used to separate the CO2 andH 2 332. - Flue gases produced by the various combustion processes may also be used in ways to extract additional energy. The
flue gas 342 from the combustion turbine is augmented by mixed gas fuel and used in a duct burner to provide heat for the steammethane reformer reactor 301. The flue gas from the steammethane reformer reactor 301 is augmented by mixed gas fuel and used in a duct burner to provide energy to power theHRSG 304. Thede-energized flue gas 349 from theHGRS 304 is vented to the atmosphere. - Water taken from the output of the tube evaporator (
item 210 inFIG. 2 ) shown inFIG. 2 , is input to a water storage tank where it is then passed through the water-gas shift reactor to be heated via heat exchanger by the exothermic reaction that occurs in the water-gas shift reactor. This heated water is input to the HRSG to be turned into steam. The steam produced in the HRSG is delivered to a steam bank for distribution to the steam methane reformer reactor; the water-gas shift reactor; and the CO2 absorption apparatus. A substantial portion of the steam in the steam bank is returned to the high pressure steam separator (item 213 inFIG. 2 ) in the main plant shown inFIG. 2 . -
FIG. 4 is a partial schematic ofFIG. 3 highlighting fuel and other gas pathways. This is the same as the diagram ofFIG. 3 except the water and steam pathways are not shown so that the other pathways can be seen more clearly. -
FIG. 5 is a partial schematic of Figure highlighting water and steam pathways. This is the same as the diagram ofFIG. 3 except only the water and steam pathways are shown so that they can be seen more clearly. -
FIG. 6 is a schematic of a pre-combustion CO2 capture process integrated into a steam methane reforming and water-gas shift process. This is a pre-combustion CO2 capture method integrated into the steam methane reforming and water-gas shift process in which natural gas is converted to CO2 and H2. An alkali and/or an alkaline earth metal oxide, which is preferably a mixture of magnesium oxide and calcium oxide, from a first separation hopper is added to the CO2 and H2 and sent through a fluid bed reactor where the mixture is converted to gas stream of H2 carrying alkali and/or an alkaline earth metal (e.g. magnesium and calcium) carbonates. As will be appreciated, most of the alkali and/or an alkaline earth metal oxides react with carbon dioxide to form alkali and/or an alkaline earth metal carbonates. Preferably at least most and even more preferably at least about 85% of the H2 is removed in a second separation hopper to form a molecular hydrogen-rich gas that is preferably substantially free and even more preferably contains no more than about 10 mole % carbon dioxide and fossil carbon. The carbonates are added to a clean CO2 stream (which is preferably substantially free of molecular hydrogen and even more preferably includes no more than about 15 mole % molecular hydrogen) and sent through a heat exchanger in the steam methane reformer where the alkali and/or an alkaline earth metal carbonates are calcined into alkali and/or an alkaline earth metal oxides. These are returned to the first separation hopper, where preferably most, and even more preferably at least about 85% of the CO2 is removed and sent to a cool down apparatus. A portion of the cooled CO2 is sent to a compressor for subsequent EOR operations or for sale or for sequestering. The remainder of the CO2 is recycled through the system where it is added to the alkali and/or an alkaline earth metal carbonates to repeat the CO2 capture cycle. - Utility-grade
natural gas 621 is input into asteam methane reformer 601 which produces primarily carbon monoxide (CO) and hydrogen (H2). This is an endothermic reaction which is operated at temperatures in the approximate range of about 850° C. to 1,100° C. The carbon monoxide and hydrogen gases are sent to a water-gas shift reactor 602 where preferably at least most, and even more preferably at least about 85% of the CO is converted to carbon dioxide (CO2) by an exothermic reaction forming an output stream of carbon dioxide and hydrogen. In one configuration of the present invention, a mixture of dry magnesium oxide (MgO) and calcium oxide (CaO) is added to this gas stream and is processed through afluid bed reactor 607 so that most of the carbon dioxide is reacted to form magnesium carbonate (MgCO3) and calcium carbonate (CaCO3). The combination of magnesium carbonate and calcium carbonate allows the capture process to occur in minutes. The proportions of magnesium carbonate and calcium carbonate are typically those found in dolomite. The stream of magnesium carbonate, calcium carbonate and hydrogen is transported, with the hydrogen now acting as the carrier fluid, and input into aseparation hopper 608 where at least most of themolecular hydrogen 623 is removed and the solid magnesium carbonate and calcium carbonate are stored. Some additional magnesium carbonate andcalcium carbonate 626 are added to the recovered magnesium carbonate and calcium carbonate to allow the mixture to be recycled with full potency as described in the paper “SEM Analysis Application to Study CO2 Capture by Means of Dolomite”, Katia Gallucci, Ferdinando Paolini, Luca Di Felice, Claire Courson, Pier Ugo Foscolo and Alain Kiennemann published in the Open-Access Journal for the Basic Principles of Diffusion Theory, Experiment and Application, 2007. Their experimental studies show that calcined dolomite is a good sorbent of CO2 with CaO re-carbonating at a temperature of about 800° C. It is also noted that it is possible to calcine dolomite at this same approximate temperature with adequate gas flow. The amount of conversion of CaO from CaCO3 and MgO from MgCO3 decreases with the number of calcination/re-carbonation cycles as the dolomite degrades. - This process ultimately produces clean CO2. Some of this is diverted and compressed in compressor 606 in preparation for sequestration or use in
EOR operations 622. The remainder is added viapath 623 to a stream of magnesium carbonate and calcium carbonate fromseparation hopper 608 to act as a carrier fluid. This stream is then input into a separate heat exchanger that forms a part of thesteam methane reformer 601 where the magnesium carbonate and calcium carbonate are calcined to magnesium oxide and calcium oxide by the heat generated insteam methane reformer 601. Additional carbon dioxide is generated during this process. The stream of carbon dioxide, magnesium carbonate and calcium carbonate is input into asecond separation hopper 603 where the CO2 is separated and sent to a CO2 cool downapparatus 604 prior to compressing and sequestering. As can be appreciated this carbon dioxide can also be sold as a product or used in EOR operations. - The advantage of this process is that the magnesium oxide and calcium oxide act as a sorbent to bind carbon dioxide to form magnesium carbonate and calcium carbonate. The magnesium carbonate and calcium carbonate are then reduced by heat to form magnesium oxide, calcium oxide and carbon dioxide which can readily be captured. Some of the carbon dioxide is sequestered and some is used to form the gas stream that entrains and carries the magnesium oxide and calcium oxide through the fluid bed reactor and also entrains and carries the magnesium carbonate and calcium carbonate through the heat exchanger in the steam methane reformer. This process is possible because the temperature for steam reforming and for calcination are approximately the same and so can be carried out in a common apparatus.
-
FIG. 7 is schematic of the present invention showing the principal elements of an innovative portion of an integrated SAGD operation (the carbon extraction plant) with the pre-combustion CO2 capture process ofFIG. 6 .FIG. 7 is similar toFIG. 3 , except the CO2 absorption facility is replaced by the pre-combustion CO2 capture process ofFIG. 6 . As inFIG. 6 , the pre-combustion capture system is integrated in with the steam methane reformer reactor. - In
FIG. 7 ,natural gas 731 enters the carbon extraction plant and a first portion is reformed by the steammethane reformer reactor 701 and water-gas shift reactor 702 to produce carbon dioxide andmolecular hydrogen 732. The carbon dioxide is captured using the method disclosed inFIG. 6 and then compressed to 1,000 psi and stored for further use (for example, for sale, for EOR or for sequestering). Some of the molecular hydrogen 735 is diverted and mixed with a second portion of the natural gas brought into the carbon extraction plant to produce a mixed gas of about 60% natural gas and about 40% hydrogen. This mixed gas is used to power acombustion turbine 706 which generates electrical power output. Using duct burners, for example, this mixed gas is also used to power: the steammethane reformer reactor 701; thefluid bed reactor 710; and a heat recovery steam generator (“HRSG”) 704 which produces steam from water input which, in turn, comes from the output of the tube evaporator shown inFIG. 2 . This steam from the HRSG is used in the steammethane reformer reactor 701 and water-gas shift reactor 702. The steam not utilized in the reforming/water-gas shift process is returned to the high pressure steam separator shown inFIG. 2 . An electrical motor is used to drivepower turbine 714 which, in turn, drives acompressor 715 which compresses thecarbon dioxide 737 to about 1,000 psi. The remainder of the hydrogen produced 736 is sent out of the carbon extraction plant and mixed with the natural gas that by-passed the carbon extraction plant to form a second mixed gas fuel (typically about 60% natural gas and about 40% hydrogen) that is used in the burners of the steam drum generators shown inFIG. 2 . -
Natural gas 731, used as the primary fuel to power the operation, is input as shown. Some of thenatural gas 731 is mixed with molecular hydrogen (“H2”) to form a mixed gas fuel. The remainder of thenatural gas 731 is sent through aheat exchanger 706 to be heated by the output gases from the water-gas shift reactor 702 and then to pick up more heat from the output gases from the steammethane reformer reactor 701 and is then fed into the steammethane reformer reactor 701 to be combined with steam and reformed into syn gas. Syn gas is carbon monoxide (“CO”) and hydrogen molecular (“H2”) with some carbon dioxide (“CO2”). The output of the steammethane reformer reactor 701 is sent to the water-gas shift reactor 702 where it is combined with steam to form primarily carbon dioxide (“CO2”) and molecular hydrogen (“H2”) 732. - A portion of utility-grade
natural gas 731 is input into asteam methane reformer 701 which produces primarily carbon monoxide (CO) and molecular hydrogen (H2). The carbon monoxide and molecular hydrogen gases are sent to a water-gas shift reactor 702 where most of the CO is converted to CO2 by an exothermic reaction forming an output stream of carbon dioxide and molecular hydrogen. In the present invention, a mixture of dry magnesium oxide (MgO) and calcium oxide (CaO) is added to this gas stream and is processed through afluid bed reactor 710 so that most of the carbon dioxide is reacted to form magnesium carbonate (MgCO3) and calcium carbonate (CaCO3). The stream of magnesium carbonate, calcium carbonate and molecular hydrogen is transported, with the molecular hydrogen now acting as the carrier fluid, and input into aseparation hopper 712 where the molecular hydrogen is removed and the solid magnesium carbonate and calcium carbonate are stored. Some additional magnesium carbonate and calcium carbonate are added to the recovered magnesium carbonate and calcium carbonate to allow the mixture to be recycled with full potency. - This process ultimately produces clean CO2. Some of this is diverted and compressed in
compressor 715 in preparation for sequestration or use inEOR operations 737. The remainder is added via path 723 to a stream of magnesium carbonate and calcium carbonate fromseparation hopper 708 to act as a carrier fluid. This stream is then input into a separate heat exchanger that forms a part of thesteam methane reformer 701 where the magnesium carbonate and calcium carbonate are calcined to magnesium oxide and calcium oxide by the heat generated insteam methane reformer 701. Additional carbon dioxide is generated during this process. The stream of carbon dioxide, magnesium carbonate and calcium carbonate is input into asecond separation hopper 708 where the CO2 is separated and sent to a CO2 cool downapparatus 709 prior to compressing and sequestering. As can be appreciated this carbon dioxide can also be sold as a product or used in EOR operations. - Flue gases produced by the various combustion processes are also used in ways to extract addition energy. The flue gas from the combustion turbine is augmented by mixed gas fuel and used in a duct burner to provide heat for the steam methane reformer reactor. The flue gas from the steam methane reformer reactor is augmented by mixed gas fuel and used in a duct burner to provide the power to drive the second turbine which operates the compressor. The flue gas from the second turbine is augmented by mixed gas fuel and used in a duct burner to provide energy to power the HRSG. The flue gas from the HGRS is vented to the atmosphere. Although not shown, the flue gases from the heat recovery steam generator may be treated by a post combustion carbon dioxide capture process.
- Water taken from the output of the evaporator shown in
FIG. 2 , is input to a water storage tank where it is then passed through the water-gas shift reactor to be heated via heat exchange by the exothermic reaction that occurs in the water-gas shift reactor. This heated water is input to the HRSG to be turned into steam. The steam produced in the HRSG is delivered to a steam bank for distribution to the steam methane reformer reactor; and the water-gas shift reactor. A substantial portion of the steam in the steam bank is returned to the high pressure steam separator in the main plant shown inFIG. 2 . - A number of variations and modifications of the invention can be used. As will be appreciated, it would be possible to provide for some features of the invention without providing others. For example, the carbon extraction plant could be used in conjunction with an electrical power generating plant to form an energy efficient facility run on natural gas where a portion of the natural gas is reformed to eliminate some fossil carbon.
- The present invention, in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, sub-combinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure. The present invention, in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, for example for improving performance, achieving ease and/or reducing cost of implementation.
- The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the invention are grouped together in one or more embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.
- Moreover though the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.
Claims (10)
1.-8. (canceled)
9. A system, comprising:
an input to receive a gas stream comprising primarily methane;
a gas separator to remove a first portion of the gas stream from a second portion of the gas stream;
a steam methane reformer reactor to convert the first portion of the gas stream to a reformed gas comprising primarily molecular hydrogen and carbon monoxide;
a water-gas shift reactor to convert the reformed gas into a reformed and water-gas shifted gas comprising primarily carbon dioxide and molecular hydrogen;
a carbon separator to remove, from the reformed and water-gas shifted gas, at least most of the carbon dioxide to form a product gas; and
a gas combiner to combine the product gas with the second portion of the gas stream to form a mixed gas, whereby a carbon content of the mixed gas is reduced relative to the received gas stream;
wherein the carbon separator performs at least the following operations:
contact the reformed and water-gas shifted with an alkali and/or an alkaline earth metal oxide to form alkali and/or an alkaline earth metal carbonates and molecular hydrogen;
remove, from the reformed and water-gas shifted gas, at least most of the alkali and/or an alkaline earth metal carbonates to form the product gas comprising at least most of the molecular hydrogen and substantially free of carbon dioxide;
pass the alkali and/or an alkaline earth metal carbonates through a heat exchanger in fluid communication with the water-gas shift reactor, to reform the alkali and/or an alkaline earth metal oxide and carbon dioxide, the carbon dioxide being substantially free of molecular hydrogen.
10. The system of claim 9 , wherein the gas stream is pipeline quality natural gas, wherein the second gas stream is combusted by a turbine to generate electricity, and wherein the removed carbon dioxide is utilized to avoid releasing carbon dioxide into the atmosphere.
11. The system of claim 10 , wherein the steam methane reformer reactor heats the first portion of the gas stream to a temperature ranging from about 850° C. to about 1100° C., wherein the water-gas shift reactor comprises at least one of a high temperature water-gas shift reactor and a low temperature water-gas shift reactor, and wherein the reformed gas comprises from about 25 to about 95 mole percent molecular hydrogen and from about 5 to about 25 mole percent carbon monoxide.
12. The system of claim 9 , wherein water is heated to a temperature of from about 50° C. to about 300° C. by energy released by the water-gas shift reactor and wherein the heated water is used as the steam in the water-gas shift reactor.
13. The system of claim 9 , further comprising:
a combustion gas turbine operated by at least a portion of the mixed gas stream to produce electrical energy.
14. (canceled)
15. The system of claim 9 , wherein at least a portion of the product gas is passed through a heat exchanger to transfer, to the at least a portion of the product gas, heat from the water-gas shift reaction, wherein the heated at least a portion of the product gas is fed to the reformer to form the synthetic gas.
16. The system of claim 9 , wherein the mixed gas comprises no more than about 80% of the carbon present in the received gas stream.
17.-21. (canceled)
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017190066A1 (en) * | 2016-04-29 | 2017-11-02 | Fuelcell Energy, Inc. | Carbon dioxide capturing steam methane reformer |
US10465305B2 (en) | 2015-11-17 | 2019-11-05 | Fuelcell Energy, Inc. | Hydrogen and carbon monoxide generation using an REP with partial oxidation |
US10608272B2 (en) | 2015-11-16 | 2020-03-31 | Fuelcell Energy, Inc. | System for capturing CO2 from a fuel cell |
US10680265B2 (en) | 2015-11-16 | 2020-06-09 | Fuelcell Energy, Inc. | Energy storage using an REP with an engine |
US10892507B2 (en) | 2014-01-31 | 2021-01-12 | Fuelcell Energy, Inc. | Reformer-electrolyzer-purifier (REP) assembly for hydrogen production, systems incorporating same and method of producing hydrogen |
US10897055B2 (en) | 2017-11-16 | 2021-01-19 | Fuelcell Energy, Inc. | Load following power generation and power storage using REP and PEM technology |
US11043684B2 (en) | 2015-11-17 | 2021-06-22 | Fuelcell Energy, Inc. | Fuel cell system having enhanced CO2 capture |
US11339333B2 (en) | 2016-04-21 | 2022-05-24 | Fuelcell Energy, Inc. | Fluidized catalytic cracking unit system with integrated reformer-electrolyzer-purifier |
US11495806B2 (en) | 2019-02-04 | 2022-11-08 | Fuelcell Energy, Inc. | Ultra high efficiency fuel cell power generation system |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080078552A1 (en) * | 2006-09-29 | 2008-04-03 | Osum Oil Sands Corp. | Method of heating hydrocarbons |
US8176982B2 (en) | 2008-02-06 | 2012-05-15 | Osum Oil Sands Corp. | Method of controlling a recovery and upgrading operation in a reservoir |
WO2011057122A1 (en) * | 2009-11-06 | 2011-05-12 | Verdeo Group, Inc. | Integrated system for the extraction, incineration and monitoring of waste or vented gases |
CA2735061C (en) | 2010-08-24 | 2017-07-18 | Kemex Ltd. | An improved water recovery system sagd system utilizing a flash drum |
WO2012024765A1 (en) | 2010-08-24 | 2012-03-01 | Kemex Ltd. | Vapour recovery unit for steam assisted gravity drainage (sagd) system |
CA2735097C (en) | 2010-08-24 | 2020-03-31 | Kemex Ltd. | A contaminant control system in an evaporative water treating system |
US10435307B2 (en) | 2010-08-24 | 2019-10-08 | Private Equity Oak Lp | Evaporator for SAGD process |
MX2013008726A (en) | 2011-01-27 | 2013-12-16 | 1Nsite Technologies Ltd | Compact evaporator for modular portable sagd process. |
MX2013008727A (en) * | 2011-01-28 | 2013-12-09 | 1Nsite Technologies Ltd | Modular transportable system for sagd process. |
US9897309B2 (en) * | 2011-07-19 | 2018-02-20 | Cleaver-Brooks, Inc. | Forced circulation steam generator |
US8899326B2 (en) * | 2011-07-19 | 2014-12-02 | Cleaver-Brooks, Inc. | Oil recovery process |
US9938861B2 (en) * | 2013-02-21 | 2018-04-10 | Exxonmobil Upstream Research Company | Fuel combusting method |
US10557338B2 (en) | 2013-09-18 | 2020-02-11 | 1234 10Th Street Llc | Reducing the carbon emissions intensity of a fuel |
CA2879257C (en) | 2014-01-21 | 2022-11-15 | Kemex Ltd. | Evaporator sump and process for separating contaminants resulting in high quality steam |
DE102014223427A1 (en) * | 2014-11-17 | 2016-05-19 | Hydrogenious Technologies Gmbh | Method and plant for generating and storing hydrogen |
US11255777B2 (en) * | 2018-06-04 | 2022-02-22 | Daniel W Chambers | Automated remote gas monitoring and flare control system |
US10850314B2 (en) * | 2018-06-04 | 2020-12-01 | Daniel W. Chambers | Remote gas monitoring and flare control system |
IT201800021556A1 (en) * | 2018-12-31 | 2020-07-01 | Archimede S R L | PROCEDURE FOR ENRICHMENT OF A LIGHT HYDROCARBE, PARTICULARLY NATURAL GAS, IN SUPERCRITICAL WATER |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060243448A1 (en) * | 2005-04-28 | 2006-11-02 | Steve Kresnyak | Flue gas injection for heavy oil recovery |
Family Cites Families (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US604330A (en) * | 1898-05-17 | Mining apparatus | ||
US1660187A (en) * | 1920-10-08 | 1928-02-21 | Firm Terra Ag | Method of winning petroleum |
US1520737A (en) * | 1924-04-26 | 1924-12-30 | Robert L Wright | Method of increasing oil extraction from oil-bearing strata |
US1660818A (en) * | 1924-05-07 | 1928-02-28 | Standard Oil Dev Co | Apparatus for recovering oil |
US1634236A (en) * | 1925-03-10 | 1927-06-28 | Standard Dev Co | Method of and apparatus for recovering oil |
FR631558A (en) * | 1926-04-03 | 1927-12-22 | Improvements in magnetic and radio direction finding | |
US1811560A (en) * | 1926-04-08 | 1931-06-23 | Standard Oil Dev Co | Method of and apparatus for recovering oil |
US1735012A (en) * | 1926-10-05 | 1929-11-12 | Rich John Lyon | Process and means for extracting petroleum |
US1722679A (en) * | 1927-05-11 | 1929-07-30 | Standard Oil Dev Co | Pressure method of working oil sands |
US1735481A (en) * | 1927-09-17 | 1929-11-12 | Standard Oil Dev Co | Flooding method for recovering oil |
US1936643A (en) * | 1929-12-10 | 1933-11-28 | James S Abererombie | Outside pipe cutter |
US1816260A (en) * | 1930-04-05 | 1931-07-28 | Lee Robert Edward | Method of repressuring and flowing of wells |
US1852717A (en) * | 1930-09-08 | 1932-04-05 | Union Oil Co | Gas lift appliance for oil wells |
US1910762A (en) * | 1932-03-08 | 1933-05-23 | Union Oil Co | Gas lift apparatus |
US2148327A (en) * | 1937-12-14 | 1939-02-21 | Gray Tool Co | Oil well completion apparatus |
US2823752A (en) * | 1955-08-30 | 1958-02-18 | Worthington Corp | Method and arrangement of apparatus for oil recovery |
US3833059A (en) * | 1973-02-12 | 1974-09-03 | Motco Inc | Hot gas apparatus for recovery of oil values |
US3946810A (en) * | 1973-05-24 | 1976-03-30 | The Ralph M. Parsons Company | In situ recovery of hydrocarbons from tar sands |
US3922148A (en) * | 1974-05-16 | 1975-11-25 | Texaco Development Corp | Production of methane-rich gas |
FR2542004B1 (en) * | 1983-03-02 | 1985-06-21 | British Petroleum Co | ELECTRICALLY ASSISTED CONVERSION PROCESS OF HEAVY CARBON PRODUCTS |
US4545435A (en) * | 1983-04-29 | 1985-10-08 | Iit Research Institute | Conduction heating of hydrocarbonaceous formations |
US4682471A (en) * | 1985-11-15 | 1987-07-28 | Rockwell International Corporation | Turbocompressor downhole steam-generating system |
DE4131976A1 (en) * | 1991-09-25 | 1993-04-01 | Ross Europa Gmbh | ARRANGEMENT FOR RECYCLING HYDROCARBONS IN FUEL REFUELING SYSTEMS |
US5375539A (en) * | 1992-09-21 | 1994-12-27 | Rippberger; Mark L. | Efficient removal of volatile compounds from soil or water |
US5656136A (en) * | 1993-11-12 | 1997-08-12 | Pool Company | Method of transporting and heating a liquid used for treating oil and gas wells or pipeline systems |
US5416245A (en) * | 1993-11-12 | 1995-05-16 | Integrated Energy Development Corp. | Synergistic process for the production of methanol |
US5516967A (en) * | 1995-01-30 | 1996-05-14 | Chemisar Laboratories Inc. | Direct conversion of methane to hythane |
JP4037475B2 (en) * | 1996-09-04 | 2008-01-23 | 忠弘 大見 | Method for treating exhaust gas containing halogen compounds |
US7066973B1 (en) * | 1996-08-26 | 2006-06-27 | Nuvera Fuel Cells | Integrated reformer and shift reactor |
JP3129670B2 (en) * | 1997-02-28 | 2001-01-31 | 三菱電機株式会社 | Fuel reformer |
US6190536B1 (en) * | 1998-05-22 | 2001-02-20 | Membrane Technology And Research, Inc. | Catalytic cracking process |
AU5568099A (en) * | 1998-08-18 | 2000-03-14 | United States Department Of Energy | Method and apparatus for extracting and sequestering carbon dioxide |
US7428926B2 (en) * | 1999-05-07 | 2008-09-30 | Ge Ionics, Inc. | Water treatment method for heavy oil production |
US6399030B1 (en) * | 1999-06-04 | 2002-06-04 | The Babcock & Wilcox Company | Combined flue gas desulfurization and carbon dioxide removal system |
US6230814B1 (en) * | 1999-10-14 | 2001-05-15 | Alberta Oil Sands Technology And Research Authority | Process for enhancing hydrocarbon mobility using a steam additive |
US6443229B1 (en) * | 2000-03-23 | 2002-09-03 | Daniel S. Kulka | Method and system for extraction of liquid hydraulics from subterranean wells |
US6387337B1 (en) * | 2000-07-14 | 2002-05-14 | The United States Of America As Represented By The United States Department Of Energy | Carbon dioxide capture process with regenerable sorbents |
CA2422885C (en) * | 2000-09-22 | 2010-01-12 | Harber Supply Company, L.L.C. | Hand-held vessel |
US7426489B2 (en) * | 2000-11-01 | 2008-09-16 | International Carbon Bank And Exchange, Inc. | Method and system for banking and exchanging emission reduction credits |
CA2325777C (en) * | 2000-11-10 | 2003-05-27 | Imperial Oil Resources Limited | Combined steam and vapor extraction process (savex) for in situ bitumen and heavy oil production |
CA2342955C (en) * | 2001-04-04 | 2005-06-14 | Roland P. Leaute | Liquid addition to steam for enhancing recovery of cyclic steam stimulation or laser-css |
US6591908B2 (en) * | 2001-08-22 | 2003-07-15 | Alberta Science And Research Authority | Hydrocarbon production process with decreasing steam and/or water/solvent ratio |
US20030188863A1 (en) * | 2002-04-05 | 2003-10-09 | Eugene Hooper And Britt Gilbert | Carbon dioxide pipeline |
US6616967B1 (en) * | 2002-04-15 | 2003-09-09 | Texas Instruments Incorporated | Method to achieve continuous hydrogen saturation in sparingly used electroless nickel plating process |
WO2004076346A2 (en) * | 2003-02-24 | 2004-09-10 | Texaco Development Corporation | Diesel steam reforming with co2 fixing |
US20040249732A1 (en) * | 2003-04-14 | 2004-12-09 | Drummond Stephen M. | Systems and methods for trading emission reduction benefits |
WO2005053831A2 (en) * | 2003-11-26 | 2005-06-16 | Cabot Corporation | Fuel reformer catalyst and absorbent materials |
CA2462359C (en) * | 2004-03-24 | 2011-05-17 | Imperial Oil Resources Limited | Process for in situ recovery of bitumen and heavy oil |
NO20043198L (en) * | 2004-07-27 | 2006-01-30 | Teekay Norway As | Procedure for supplying filler gas to a cargo tank |
US7497191B2 (en) * | 2006-02-06 | 2009-03-03 | Eden Innovations Ltd. | System and method for producing, dispensing, using and monitoring a hydrogen enriched fuel |
US7654320B2 (en) * | 2006-04-07 | 2010-02-02 | Occidental Energy Ventures Corp. | System and method for processing a mixture of hydrocarbon and CO2 gas produced from a hydrocarbon reservoir |
US20070277438A1 (en) * | 2006-05-30 | 2007-12-06 | Brehon Energy Plc | System and method for producing a hydrogen enriched fuel |
US7691788B2 (en) * | 2006-06-26 | 2010-04-06 | Schlumberger Technology Corporation | Compositions and methods of using same in producing heavy oil and bitumen |
US8474531B2 (en) * | 2009-11-24 | 2013-07-02 | Conocophillips Company | Steam-gas-solvent (SGS) process for recovery of heavy crude oil and bitumen |
-
2009
- 2009-07-07 WO PCT/IB2009/006522 patent/WO2010004425A2/en active Application Filing
- 2009-07-07 US US12/498,895 patent/US20100058771A1/en not_active Abandoned
- 2009-07-07 CA CA2727766A patent/CA2727766C/en not_active Expired - Fee Related
- 2009-07-07 CA CA2822128A patent/CA2822128A1/en not_active Abandoned
-
2013
- 2013-05-15 US US13/894,554 patent/US20130251598A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060243448A1 (en) * | 2005-04-28 | 2006-11-02 | Steve Kresnyak | Flue gas injection for heavy oil recovery |
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US10608272B2 (en) | 2015-11-16 | 2020-03-31 | Fuelcell Energy, Inc. | System for capturing CO2 from a fuel cell |
US10680265B2 (en) | 2015-11-16 | 2020-06-09 | Fuelcell Energy, Inc. | Energy storage using an REP with an engine |
US10465305B2 (en) | 2015-11-17 | 2019-11-05 | Fuelcell Energy, Inc. | Hydrogen and carbon monoxide generation using an REP with partial oxidation |
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Also Published As
Publication number | Publication date |
---|---|
WO2010004425A2 (en) | 2010-01-14 |
US20100058771A1 (en) | 2010-03-11 |
WO2010004425A3 (en) | 2010-03-04 |
CA2727766A1 (en) | 2010-01-14 |
CA2822128A1 (en) | 2010-01-14 |
CA2727766C (en) | 2013-10-08 |
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