The present invention relates to a device for combustion of a carbon containing fuel in a nitrogen free atmosphere and a method for operating said device.
The device may be integrated with a power generation plant (i.e. gas turbine(s)) to obtain an energy efficient process for generation of power with reduced emission of carbon dioxide and NOx to the atmosphere. Furthermore, the device may be integrated with a chemical plant performing endothermic reactions.
Conventional combustion processes, used for carbon containing fuels, will in addition to producing the main end products carbon dioxide and water (steam), generate a considerable amount of heat (heat of combustion). A conventional combustion reaction between e.g. methane and oxygen will generate approximately 804 KJ per mol methane:
CH4+2O2—>CO2+2H2O
When this combustion process is integrated with e.g. a power generation plant (i.e. gas turbines) or a chemical plant performing endothermic reactions, it is crucial that the total energy loss from the combustion process is as low as possible.
Furthermore, due to the environmental aspects of CO2 and NOx it is crucial that the emission of these components to the atmosphere is considerably reduced compared to conventional processes. Conventional combustion processes produce an exhaust gas with a CO2-concentration between 3 and 15% dependent on the fuel and the combustion- and heat recovery process applied. The reason the concentration is this low is because air comprises about 78% by volume of nitrogen. In high-temperature combustion processes in air, nitrogen will react with oxygen and produce the environmental hazardous gas pollutant NOx.
A reduction in the emission of carbon dioxide to the atmosphere makes it necessary to either separate the carbon dioxide from the exhaust gas, or raise the concentration in the exhaust gas to levels suitable for use in different chemical processes or for injection in e.g. a geological formation for long term deposition or for enhanced recovery of oil from an oil reservoir.
CO2 can be removed from cooled exhaust gas, normally discharged at near atmospheric pressure, by means of several separation processes, e.g. chemical active separation processes, physical absorption processes, adsorption by molecular sieves, membrane separation and cryogenic techniques. Chemical absorption, for instance by means of alkanole amines, is considered as the most practical and economical method to separate CO2 from exhaust gas. These separation processes consume energy and require heavy and voluminous equipment. Applied in connection with a power generation process, these separation processes will reduce the power output with 10% or more.
An increase of the concentration of CO2 in exhaust gas from a combustion reaction to levels suitable for use in different chemical processes or for injection in e.g. a geological formation for long term deposition or for enhanced recovery of oil from an oil reservoir is possible by burning the carbon containing fuel with pure oxygen instead of air.
Commercial air separation methods (e.g. cryogenic separation or pressure swing absorption (PSA)) applied for producing pure oxygen require 250 to 300 KWh/ton oxygen produced. If these methods are used for supplying oxygen to a combustion process in a gas turbine cycle these methods will reduce the net power output from the gas turbine cycle by at least 20%. The expenses of producing oxygen in a cryogenic unit will increase the price of produced electric power substantially and may amount to as much as 50% of the cost of the electric power.
However, a less energy demanding method than these separation methods is known from the European Patent Application 658 367-A2. The patent application describes an application of a mixed conducting membrane (MCM) integrated with a gas turbine system and where the membrane separates oxygen from a heated air stream.
The mixed conducting membrane (MCM) is defined as a membrane made of materials with both ionic and electronic conductivity. The membrane selectively transports oxygen. The driving force through the membrane is proportional to the logarithmic relation between oxygen partial pressures; log (pO2(I)/pO2(II)), where (I) represents the oxygen delivering side (air) of the membrane and (II) represents the oxygen receiving side of the membrane. To keep a high transport rate (flux) of oxygen it is important to keep a low partial pressure on the oxygen receiving side.
Thus, to further improve the efficiency of this membrane process, a sweep gas is applied to reduce the partial pressure of oxygen on the oxygen receiving side of the membrane and thereby increase the flux of oxygen through the membrane; as e.g. described in U.S. Pat. No. 5,562,754 and NO-A-972632.
To obtain practical applications of mixed conducting membranes (MCM) when applied as an oxygen supplier in a combustion process the following criteria are essential:
To ensure that the driving force through the membrane is kept at a high level oxygen on the oxygen receiving side of the membrane has to be:
This implies that the device which shall perform an energy efficient combustion in a nitrogen free atmosphere must be designed to operate under process conditions as mentioned above. There remains therefore a need for such a device and a method for operating said device that is not described in the prior art.
The main object of the present invention was to provide a device effective to achieve combustion of a carbon containing fuel in a nitrogen free atmosphere.
Another object of the present invention was to provide a device effective to achieve a combustion process resulting in an exhaust gas with a high concentration of CO2 and a low concentration of NOx.
Furthermore, another object of the invention was to provide a method for operating said device.
Yet another object of the invention was to provide a plant and a method for an energy efficient generation of power.
Still yet another object of the invention was to provide a plant and a method for generation of power with reduced emission of carbon dioxide and NOx to the atmosphere.
The inventors found that the described objects were fulfilled by utilizing a device where one or more mixed conducting membrane module(s), one or more heat exchange module(s) and one or more combustion chamber(s) were enclosed within a hollow shell (a pressure vessel) defining an enclosure. The device may further be integrated with gas turbine(s) in a plant for generation of power. The device may also be integrated with a chemical plant performing an endothermic reaction to supply necessary heat to the reaction.
The mixed conducting membrane(s) (MCM) which is utilized in the device according to the present invention will at conditions described above (a) and b)) transport oxygen from an oxygen delivering gas (e.g. air) to an oxygen receiving gas. The oxygen receiving gas has a lower partial pressure of oxygen than the oxygen delivering gas. To the oxygen receiving gas a carbon rich fuel (e.g. natural gas) is added and a heat generating combustion reaction between oxygen and added fuel takes place.
Combustion of natural gas with pure oxygen will produce an exhaust gas containing the two main products carbon dioxide and water (steam). According to the present invention the exhaust gas is utilized as the oxygen receiving gas. The oxygen rich gas stream (i.e. the oxygen enriched exhaust gas) is fed to the combustion chamber and applied as oxidant in the combustion reaction. Thus, a production of the environmental harmful NOx gas is avoided.
The thermal energy produced by the combustion reaction is by means of heat exchanger(s) utilized to heat air fed to the MCM-module(s) as well as to heat oxygen depleted air leaving the MCM-module(s) before it may enter a power generation turbine or a chemical plant performing an endothermic reaction.
Thus the air stream fed to the membrane is heated without producing CO2 or NOx, in the stream. In the combustion reaction almost all oxygen is consumed and thus the exhaust gas, now having a very low partial pressure of oxygen, can be recirculated to the MCM as a sweep gas picking up oxygen before entering the combustion chamber again. Thus we have a continuous combustion. From the exhaust gas a bleed stream has to be taken out to balance the added fuel and oxygen received to prevent accumulation of mass. This bleed gas leaving the device at elevated pressure and temperature could also be fed to a power generation system (turbine). In the turbine the pressure of the bleed gas is decreased and further cooled to condense almost all steam to water. Thus the gas flow will consist mainly of carbon dioxide. This carbon dioxide gas flow has to be compressed to a pressure that allows injecting in an underground reservoir, a reservoir that could be an aquafier layer or a gas or oil reservoir. These reservoirs should be qualified for ensuring long term deposition.
As mentioned above the exhaust gas is utilized as a sweep gas to pick up oxygen in the membrane module(s) and transport oxygen to one or more combustion chambers where fuel is added. The heat generated in the exhaust gas should in an efficient way be transported to the air stream, and in such a way, that leakage between sweep gas and air is prevented or minimised to an acceptable level.
Furthermore, the inventors found that by utilizing a multiplate or a multichannel structure as a MCM-module and/or as a heat exchange module a very efficient device was achieved. Multichannel structures are found to be the most advantageous due to the fact that they can be extruded in one piece (i.e. a monolith) and thus a large surface area in one piece is obtained. Most preferably both the heat exchange module(s) and the MCM-modules are made of a ceramic material that is able to withstand the present process conditions (atmosphere, temperature and pressure).
Such structures, especially with channel diameter below 10 mm, give a very high surface area/unit volume. By preparing every second row of channels by inlet slots as described in U.S. Pat. No. 4,271,110 a simplified manifold system to every second row of channels could be achieved and thus give a low leakage rate probability between the air side and the oxygen receiving side.
To obtain a largest possible surface area for heat exchange and/or oxygen transfer (when utilized as a MCM-module), the channels should be very small and every air channel should be surrounded by (i.e. have common walls with) the other gas (i.e. sweep/exhaust gas). Such a configuration needs a very complicated system for leading the two gases (manifolding) to each adjacent channel.
According to the present invention such multichannel monolithic structures are connected or linked together in such a way that the MCM-module is installed between two heat exchange modules. Furthermore, these modules are installed in a pressure vessel hereinafter defined as the reactor. Such a system will ensure that the MCM is able to operate at a defined temperature higher than the temperature in the air stream fed to the system and below the temperature of combustion (i.e. the exhaust gas temperature from the combustion chamber).
Another important feature of the present invention is the flow pattern of the two gas streams. The first gas stream (the air stream) has a flow from inlet to outlet of the reactor that follows longitudinal to the direction of channels in the monolithic structures (i.e. heat exchangers and MCM). This means that the gas enters and leaves the open channels from the short ends and flows through an open room or closed structure that connects these ends. The second gas stream has a flow direction in and out of the side slots of the monolith, through bypass rooms or connectors to the side slot of the adjacent monolithic structures. These bypass rooms are surrounding the inner open room of the first gas.
Such a flow system of the gases will allow one of the gases, here the second gas, to leak and fill all available space or “empty” room of the reactor. The requirement for a gas tight sealing is then reduced for the first gas only to be a sealing towards the second gas (not to the “empty” space of the reactor) located at the inner coupling connectors between the monolithic structures.
This feature is very important because a controlled leakage of gas is necessary to build up and equalise the pressure inside the reactor house, and only one of the gases is allowed to leak to prevent mixing. This controlled and necessary leakage allows a flexible sealing of defined leakage rate for the bypassing connectors of the second gas. Flexibility to avoid thermal stress in connecting parts/monolithic structures is very important to prevent fatal cracks.
By filling the reactor with gas of almost the same pressure as the gas inside the monolith channels only the outer pressure shell of the reactor has to withstand the absolute or total pressure of the process. The pressure on the monolith walls is then reduced to withstand the differential pressure between the two gases (Gas 1 and Gas 2 in
The scope of the invention and its special features are as defined by the attached claims.
The invention will be further explained and envisaged in the following figures.
A part of the hot combustion product or exhaust gas (EG-010) is taken out as a bleed stream (EG-040) to prevent accumulation of mass in the reactor while the rest of the product gas is fed to the heat exchange module (H-02) and heated to the operational temperature of the membrane. In the membrane module stream (EG-020) is acting as a sweep gas. The hot and oxygen enriched sweep gas stream (EGO-020) is fed to the heat exchange module (H-01) to heat the incoming gas stream (AN-030). The heated air stream (AN-050) is entering the MCM-module (X-01) at the operational temperature of the MCM-modules (X-01). A pressure booster (I-01) has to be installed to enhance circulation in the sweep gas loop and ensure a continuous combustion. In
An external combustion chamber will also simplify the fuel (NG-010) injection system and makes it easier to upscale the device as will be shown in
According to
Gas 2 represents the gas streams (EGO-020) and (EGO-030) if the module is (H-01), the gas streams (EG-030) and (EGO-010/020) if the module is (X-01) and gas streams (EG-020) and (EG-030) if the module is (H-02).
Gas 1 follows the straight path through the channels and is thus always fed in and let out from the open rows of channels at the monolith ends. Gas 2, normally the sweep gas, is always fed in and taken out from the open slots in the side wall of the monolith structures. Since these monolithic structures preferably will be made by extrusion, all channels will be of the same length. The inlet and the outlet slots of Gas 2 must be made after extrusion by machining every second column of channels as visualised on the figure. After machining down to the preferred depth the open row of channels (made by machining) has to be closed by a sealing in such a way that a sufficient opening area for the side slot is kept (inlet and outlet for Gas 2).
The problem of preventing leakage in the manifold system of two different gases leading in and out of the multichannel monolithic structures is minimised by making these inlet and outlet slots as described and shown in
According to the present invention a channel diameter below 10 mm is used. A diameter between 1 and 8 is preferred.
(EG) is thus somewhat cooled down by (AL) in (H-02) before it enters the membrane module(s) (X-01). In (X-01) (EG) acts as a sweep gas picking up oxygen transferred through the membrane wall from the air side. The oxygen enriched sweep gas leaving (X-01), now named (EGO), is then entering the first heat exchanger (H-01) where the air stream (AN) is heated and the stream (EGO) is cooled. Thus a cooled oxygen containing sweep gas (EGO) is now returning via (I-01) to (F-01) and thus an exhaust/sweep gas loop is obtained enhancing a continuous combustion.
Either from the oxygen enriched sweep gas (EGO) or from the exhaust gas (EG) a bleed gas has to be taken out to prevent accumulation of mass in the sweep gas loop due to the oxygen transfer from the air and the addition of the fuel. Example of bleed gas outlet is shown in
Also shown in
Reactor pressure vessel 1 contains the low temperature heat exchanger 9, the high temperature heat exchanger 19 and the MCM-modules 15. Thus all other parts are built up around these units 9, 15 and 19 which ensure good heat transfer (from sweep/exhaust gas to air) and oxygen transfer (from air to sweep gas). The parts 8, 14 and 18 are used to make a round shape at the outer wall of the heat exchangers and MCM-modules to ensure less complicated sealing. These parts could also be made with channels in such a way that they can be used as heat exchangers 8 and 18 or as MCM-modules 14. The individual parts 10, 11, 12 and 13 will fit together and make the connection between the low temperature heat exchanger 9 and the MCM-modules 15 as shown in
The inlet and outlet pipes 4 and 25 may have the same shape to simplify the fabrication. Inlet pipe 4 leads the air stream to the inlet plenum made up by 7 and made in such a way that flexible sealings 5 can be mounted. The inlet pipe 4 is most preferably made of a material that also acts as a thermal barrier or lining between the hot inlet air and the outer metal pipe connected to the pressure vessel shell. This is especially important for the outlet pipe 25 in the high temperature end. Also shown are parts 6 and 22 that act as a thermal barrier or lining between exhaust/sweep gas and the flanged inlet/outlet metal pipe of the pressure vessel.
Also shown is the thermal barrier and insulation 3 between the high temperature inner parts and the outer metal wall or shell of the pressure vessel Keeping a low temperature (<500° C.) in the outer pressure shell will reduce heat loss and allow the pressure shell to be made of a common engineering material (i.e. carbon steel). By lowering the temperature, the thickness of the wall and thus also the total weight of the device is reduced. This is important for an offshore installation.
Parts 3 are also made in a shape and of such a material that it can act as support for the inner parts. 2 is a layer of a flexible material between the inner wall (pressure shell) and 3 allowing for some movement caused by thermal expansion.
According to the present invention one or more reactor units can be coupled together and share a common combustion chamber as shown in
Shown in
A part of the total fuel, (NG-030), is mixed with stream (EGO-010) in an additional combustion chamber (F-02) situated between (X-01) and (H-01) where the heat generated from this combustion will be supplied to heat exchanger (H-01) for heating incoming air. It has to be emphasized that the present invention will work without this combustion chamber (F-02) as explained in
A part of the hot exhaust gas (EG-040) is discharged as a bleed stream to prevent accumulation of mass in the exhaust/sweep gas loop. In principle the bleed gas stream (EG-040) can be discharged anywhere in the sweep gas circulation loop. For example it can be discharged in the cold end, from (EGO-030), and sent directly to a steam turbine. The exhaust gas (EG-020) is fed via the high temperature heat exchanger (H-02) to the membrane module (X-01). Acting as sweep gas, (EG-030) is receiving oxygen transported through the membrane from the air side and further transports the oxygen to the combustion chamber. Thus a closed loop with a continuous combustion of a carbon rich fuel with O2 in a CO2 and H2O rich atmosphere is obtained.
Table 1 below gives example of data for the process flows with numbers according to
A further advantage will be to have a low pressure difference (<5 bar) between the air side and the sweep gas side, preferably with somewhat higher pressure on the sweep gas side. This will ensure, in case of leakage between the stream and the sweep gas stream, that the direction of leakage will be from the sweep gas side (CO2 and H2O) into the air side. This will be less harmful than if air leaks into the combustion loop (sweep gas), especially from an environmental point of view because in case of nitrogen (air) leakage into combustion (sweep gas loop) the NOx gas could be produced.
Further, a low pressure difference between air and sweep gas side will allow designing with thinner walls in monoliths and thus better heat and oxygen (only X-01) transfer. This will also result in lower weight.
Table 1 below gives example of data for the process flows with numbers according to
(*) The oxygen flow (OX-010) is not a physical gas flow as shown in the table. Oxygen is transported through the membrane as oxygen ions and thus (OX-010) in Table 1 is for the purpose of calculation.
Number | Date | Country | Kind |
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200006690 | Dec 2000 | NO | national |
Filing Document | Filing Date | Country | Kind |
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PCT/NO01/00499 | 12/19/2001 | WO |