Patent Grant
9453644
The present invention relates to a method of generating electrical power in which a synthesis gas stream, produced in a gasifier, is combusted in an oxygen transport membrane based boiler to generate heat that is used to raise steam and that is in turn used in a steam turbine to generate electrical power. More particularly, the present invention relates to such a method in which a high pressure synthesis gas stream produced in the gasifier is indirectly heated in at least one oxygen transport membrane based partial oxidation reactor using a low pressure synthesis gas slip stream as fuel to combust with oxygen separated from a feed air stream by the oxygen transport membrane in the partial oxidation reactor and expanded in a turbine prior to being combusted in an oxygen transport membrane based boiler.
Coal-fired power plants are utilized throughout the world to generate electricity. Typically, the coal is either in a pulverized form or within a slurry is combusted to generate heat within a boiler to raise steam. The steam is passed into a steam turbine to generate electrical power. There has been recent interest in capturing carbon dioxide from power plants that use coal and other carbonaceous feed stock such as asphalt, heavy oil, petroleum coke, biomass or natural gas. An integrated gasification and combined cycle (IGCC) is proposed as a preferred method of power generation when carbon dioxide capture is required. In IGCC, gasification of fuel produces a synthesis gas containing mainly hydrogen, carbon monoxide and carbon dioxide with some amount of methane and sulfur and chloride containing impurities. In a typical gasifier the carbonaceous feed is reacted with steam and oxygen to produce the synthesis gas. Typically, the oxygen is provided to the gasifier by a cryogenic air separation unit.
In IGCC, the synthesis gas produced as a result of the gasification is typically cooled to a temperature suitable for its further processing in a water-gas shift reactor to increase the hydrogen and carbon dioxide content of the synthesis gas. The water-gas shift reactor also hydrolyzes most of the carbonyl sulfide into hydrogen sulfide. The synthesis gas is then further cooled for carbon dioxide and hydrogen sulfide separation within a solvent scrubbing plant employing physical or chemical absorption for separation of the carbon dioxide and hydrogen sulfides and carbonyl sulfide from the synthesis gas. This allows for the capture and sequestration of the carbon dioxide which is present within the synthesis gas. The resulting hydrogen-rich gas is then fed to a gas turbine that is coupled to an electrical generator to generate electricity. Heat is recovered from the cooling of the raw synthesis gas stream, from cooling the heated discharge from the water-gas shift reactor, and cooling the exhaust from the gas turbine to raise steam and to generate additional electrical power from a steam turbine.
As can be appreciated, the IGCC is environmentally very advantageous in that a clean burning synthesis gas stream is used to power the gas turbine while at the same time, the carbon dioxide produced by the gasification can be captured for use in other industrial processes, for enhanced oil recovery or for sequestration. The disadvantage of such an IGCC cycle is the high energy penalty associated with the air separation and solvent scrubbing plants. Additionally, the recovery of heat energy in several stages is inherently inefficient in that such heat recovery always involves loss and in any case, the heat is recovered at a low temperature. Lastly, the use of solvent scrubbing plants, water-gas shift reactors and gas turbines is an expensive proposition given their high capital costs.
The use of oxygen transport membrane (OTM) systems have also been contemplated in connection with boilers to generate products used to produce electricity, as disclosed in U.S. Pat. Nos. 6,394,043; 6,382,958; 6,562,104; and, more particularly U.S. Pat. Nos. 7,856,829 and 8,196,387. In such OTM based systems, oxygen is separated from the air with the use of a ceramic membrane that is capable of oxygen ion transport at elevated temperatures. The oxygen ionizes on one surface of the membrane by gaining electrons to form the oxygen ions. Under a driving force of a partial pressure differential, the oxygen ions pass through the membrane and either react with a fuel or recombine to elemental oxygen liberating the electrons used in the ionization of the oxygen.
An alternative oxygen transport membrane based system and the closest prior art for advanced power cycle systems are disclosed in U.S. Pat. Nos. 7,856,829 and 8,196,387. These prior art advanced power cycle systems require the oxygen transport membrane to operate in a high pressure environment of about 350 psig, particularly in the POx stages which directly heat the synthesis gas from the gasifier ahead of any expansion stages. One of the recognized problems associated with oxygen transport membranes is that when operating in severe environments, such as high pressure environments, the reliability of the oxygen transport membranes typically suffer resulting in more membrane failures and associated system operating downtime and maintenance costs. In addition, oxygen transport membranes that are designed to operate in higher pressure environments typically require very thick support layers thus significantly increasing the cost of the oxygen transport membranes and associated reactors.
In lieu of operating the oxygen transport membranes at such high pressures, prior art solutions contemplate regulating a portion of the high pressure gasifier stream to lower pressure levels before introduction to the oxygen transport membranes based reactors. Regulating or reducing the high pressure gasifier stream involves specialized equipment and adversely impacts the overall economics and efficiency of the oxygen transport membrane based power system. Also, the prior art solutions requires the oxygen transport membranes to operate at very low fuel utilization or conversions rates making it difficult to control the oxygen flux across the membranes, since oxygen flux is a decreasing function of the fuel utilization or fuel conversion.
What is needed therefore is a method for generating power from a high pressure gasifier stream using an oxygen transport membrane based system designed to operate at lower pressures and is more cost efficient than the current prior art oxygen transport membrane based power cycle systems and solutions. In particular, what is needed is an oxygen transport membrane based power cycle system that facilitates operation of the oxygen transport membrane at low fuel pressures with high fuel utilization or fuel conversion.
The present invention may be characterized as a method of generating electrical power comprising the steps of: (i) generating a synthesis gas stream in a gasifier; (ii) heating the synthesis gas stream via indirect heat exchange with radiant heat generated from at least one oxygen transport membrane based partial oxidation reactor; (iii) expanding the heated synthesis gas stream in at least one expansion stage; (iv) diverting a portion of the expanded synthesis gas stream to the at least one oxygen transport membrane based partial oxidation reactor where such diverted portion of the synthesis gas stream is partially oxidized with permeated oxygen from the oxygen transport membrane based partial oxidation reactor to produce a reaction product stream and the radiant heat; (v) feeding another portion of the expanded synthesis gas stream and the reaction product stream to an oxygen transport membrane based boiler where the synthesis gas stream and reaction product stream react with permeated oxygen and a source of supplemental oxygen to produce steam from a source of boiler feed water and produce a carbon dioxide containing flue gas stream; (vi) extracting energy from the steam by a steam turbine subsystem operatively associated with the oxygen transport membrane based boiler and converting the extracted energy to electrical power; and (vii) purifying the carbon dioxide containing flue gas stream to produce a carbon dioxide-rich stream.
The present invention may also be characterized as an oxygen transport membrane based advanced power cycle system comprising: (a) a source of high pressure synthesis gas; (b) at least one oxygen transport membrane based partial oxidation reactor having one or more oxygen transport membrane elements and one or more metal tubes containing the synthesis gas and disposed adjacent or juxtaposed to the one or more oxygen transport membrane elements; (c) at least one expander disposed downstream of the at least one oxygen transport membrane based partial oxidation reactor, the expander configured to expand the heated synthesis gas stream to produce energy and reduce the pressure of the synthesis gas stream; (d) a recycle conduit configured to divert a portion of the expanded synthesis gas stream to the at least one oxygen transport membrane based partial oxidation reactor where such diverted portion of the synthesis gas stream is the low pressure synthesis gas slip stream that is partially oxidized with the permeated oxygen; (e) an oxygen transport membrane based boiler having one or more oxygen transport membrane elements and one or more steam tubes containing the boiler feed water and disposed adjacent or juxtaposed to the one or more oxygen transport membrane elements in the oxygen transport membrane based boiler, and (f) a steam turbine subsystem operatively associated with the oxygen transport membrane based boiler and configured to convert the steam to electrical power. Optionally, the at least one oxygen transport membrane based partial oxidation reactor and the at least one an oxygen transport membrane based boiler may be disposed in an integrated reactor housing to reduce capital costs associated with the system.
The at least one oxygen transport membrane based partial oxidation reactor is configured to partially oxidize a low pressure synthesis gas slip stream with oxygen permeated through one or more oxygen transport membrane elements to produce a reaction product stream and the first source of radiant heat; and wherein the radiant heat is used to heat the synthesis gas stream in adjacent metal tubes. The oxygen transport membrane based boiler configured to heat the boiler feed water in the steam tubes to produce steam via indirect heat exchange with a second source of radiant heat generated from a combustion of the low pressure synthesis gas with oxygen permeated through the one or more oxygen transport membrane elements in the oxygen transport membrane based boiler. The oxygen transport membrane based boiler is further configured to combust any expanded synthesis gas stream with a source of supplemental oxygen, such as cryogenically produced oxygen from an air separation unit, to produce a carbon dioxide containing flue gas and to further heat the boiler feed water in the steam tubes to produce steam.
Some embodiments of the oxygen transport membrane based advanced power cycle system and associated methods of generating electrical power may also include a carbon dioxide purification subsystem configured to purify the carbon dioxide containing flue gas stream and produce a carbon dioxide-rich stream. Other embodiments of the oxygen transport membrane based advanced power cycle system may also include an air supply and preheat subsystem that includes an oxygen containing feed stream; a regenerative air preheater configured to heat the oxygen containing feed stream; a plurality of conduits for supplying the heated oxygen containing feed stream from the regenerative air preheater to the oxygen transport membrane based partial oxidation reactors and the oxygen transport membrane based boiler; and a plurality of return conduits configured to return a heated, oxygen depleted stream from the oxygen transport membrane based partial oxidation reactors and the oxygen transport membrane based boiler to the regenerative air preheater to heat oxygen containing feed stream.
While the specification concludes with claims distinctly pointing out the subject matter that applicants regard as their invention, it is believed that the invention will be better understood when taken in connection with the accompanying drawings in which:
In a broad sense, the illustrated advanced power cycle system 10 comprises an air supply and preheating subsystem 11; one or more oxygen transport membrane based partial oxidation stages 21; one or more expansion stages 31; an oxygen transport membrane based boiler and power generation subsystem 41; and a carbon dioxide purification unit or subsystem 51.
With reference to
As the heated feed air stream 15 flows along the oxidant-side surface of the heated OTM elements or tubes 28, 48 in the OTM POx reactors 22, 24 and OTM boiler 40, the feed air stream 15 becomes generally depleted of oxygen and heated as a result of convective heat transfer from the OTM elements or tubes 28, 48 and the passing air stream. Modeling of the presently disclosed advanced power cycle system 10 shows that approximately 70% or more of the oxygen within the feed air stream 15 is transported or permeated across the OTM elements or tubes 28, 48. The residual streams are heated, oxygen-depleted streams 16 that exit the OTM boiler 40 or OTM POx reactors 22, 24 where they are combined and preferably used to preheat the incoming feed air stream 14, via a ceramic regenerative air preheater 13.
It should be appreciated that in the present illustrated embodiment, no standard flue gas-to-air preheater exists because air preheating for the feed air stream 14 is handled separately in a regenerative heat exchanger 13, preferably a ceramic regenerator, although the ceramic regenerative heat exchanger 13 could be any type of thermal regenerator that uses a high temperature capable medium to store and transfer heat. Separate air preheaters for each of the OTM POx reactors 22, 24 and for the OTM boiler 40 are not required, although use of multiple regenerators or a modularized regenerator may be used in lieu of the illustrated single regenerator. The illustrated air supply and preheat subsystem 11 also includes a blower or fan 17 needed to convey an oxygen containing feed streams 14 through the single regenerative air preheater 13, downstream and OTM POx reactors 22, 24 and OTM boiler 40.
The illustrated advanced power cycle system 10 of
Specifically, the one or more oxygen transport membrane based partial oxidation stages is comprised of a pair of OTM POx reactors 22, 24 that operate at lower fuel pressures and higher fuel utilization rates than prior art advanced power cycle systems. The low fuel pressure and high fuel utilization is achieved by recycling a portion of the expanded synthesis gas streams, referred to as the synthesis gas slip stream 27, and combusting the low pressure synthesis gas slip stream 27 with the permeated oxygen 30 in the OTM POx reactors 22, 24. In the illustrated embodiment, the first OTM POx reactor 22 is used to combust enough of the synthesis gas slip stream 27 to raise the temperature of the high pressure synthesis gas stream 23 to about 900° C. or higher. The heated synthesis gas stream 23 is then expanded using a turbo-expander 32 to an intermediate pressure and is directed or fed through a second OTM POx reactor 24. The second OTM POx reactor 24 again oxidizes only enough of the low pressure synthesis gas slip stream 27 with permeated oxygen 30 to further heat the intermediate pressure synthesis gas stream 25 to a temperature of about 930° C. or higher. The intermediate pressure heated synthesis gas stream 25 is then directed or fed through a second turbo-expander 34 and is expanded to near atmospheric pressure. Using the two expansion stages, rather than a single expansion stage, improves the efficiency of the advanced power cycle system 10. In some embodiments, the pair of turbo-expanders 32, 34 may be operatively coupled to one or more generators configured to recover supplemental electrical power from the one or more expansion stages.
In the proposed arrangement of the advanced power cycle system 10, the expansion power of each turbine unit or turbo-expander 32, 34 is similar to that of a General Electric Frame 5 Gas Turbine. Expander performance end efficiency was estimated to be about 85% for the first expansion stage and about 92% for the second expansion stage. As discussed above, a portion of the further expanded synthesis gas 25 is split off downstream of the second turbo-expander 34 and sent back or recycled to the OTM POx reactors 22, 24 to be used as the low pressure synthesis gas slip stream 27.
The OTM POx reactors 22, 24 preferably comprise a plurality of OTM elements or tubes 28 configured to separate and transport oxygen ions from the heated oxygen containing feed stream 15 contacting the oxidant side to the permeate or reactive side of the OTM elements or tubes 28 where the oxygen ions are recombined to form oxygen. The permeated oxygen 30 reacts with a portion of the low pressure synthesis gas slip-stream 27 to produce supplemental reaction products 29 and, more importantly, heat. The heat generated from the partial oxidation of the permeated oxygen 30 and low pressure synthesis gas slip stream 27 is radiated to metallic tubes 26 that contain the high pressure synthesis gas stream disposed near or juxtaposed to the OTM elements or tubes 28. Any unused portion of synthesis gas slip stream 27 together with the reaction products 29 from the partial oxidation occurring within the OTM POx reactors 22, 24 are then mixed back in with the further expanded synthesis gas stream 35 that is fed to the OTM boiler 40.
Advantageously, the recycling of low pressure synthesis gas slip-stream 27 to the permeate or reactive side of the OTM elements or tubes 28 combined with the low pressure air feed stream 15 on the oxidant side OTM elements or tubes 28, 48 allows for the OTM based POx reactors 22, 24 and OTM boiler 40 to operate at low pressure on both sides of the oxygen transport membranes which decreases system costs and minimizes risks associated with operating the OTM ceramic materials under high pressure gradients. Since the recycled synthesis gas slip stream 27 is a low pressure stream, the operational environment of the OTM POx reactors 22, 24 is less severe than prior art systems and the OTM elements or tubes 28 are generally less costly to manufacture. The relative flows of the synthesis gas slip stream 27 directed to each of the POx reactors 22, 24 are preferably controlled to optimize fuel utilization of the advanced power cycle system 10.
Following the second turbo-expander 34, the still mostly un-oxidized and low pressure synthesis gas stream 35 flows to the OTM boiler 40 where a plurality of OTM elements or tubes 48 are disposed that provide or supply the oxygen required to support the combustion of up to about 95% of the low pressure synthesis gas stream 35. In the OTM boiler 40, steam tubes 46 are also arranged proximate or juxtaposed to the OTM elements or tubes 48 for removal of energy needed to keep the gas and surface temperatures of the OTM elements or tubes 48 at around 1000° C. The majority of the synthesis gas stream 35 flowing through the OTM boiler 40 is combusted at or near atmospheric pressure using the permeated oxygen 30 and the resulting heat is used to raise steam to facilitate the removal of energy from the system.
A non-traditional boiler arrangement is preferably used in order to accommodate both the OTM surface temperatures and the steam tube surface temperatures. The section of the boiler containing OTM elements or tubes 48 should preferably be maintained at between 900° C. and 1100° C., and more preferably at about 1000° C. for optimal membrane performance. In addition to the OTM element temperatures, the degree of synthesis gas combustion via the OTM elements or tubes 28, 48 is also an important optimization variable. Thus, use of oxidation catalysts within the OTM elements or tubes may be considered. Depending on OTM oxygen flux and across the OTM elements or tubes 28, 48 and the amount of recycled low pressure synthesis gas slip stream 27 fed to the reactant side of the OTM POx reactors 22, 24, it is estimated that between about 70% and 95% of the total synthesis gas stream may be reacted or combusted with permeated oxygen 30 from OTM elements or tubes 28, 48 the majority of which occurs in OTM boiler 40.
While combustion of the low pressure synthesis gas stream 35 with permeated oxygen 30 Following the last section of OTM elements or tubes 48 in the OTM boiler 40, some synthesis gas still remains unreacted in the gas stream, typically between about 5% and 30% of the original synthesis gas stream 20. A source of oxygen 60 from a cryogenic air separation plant (not shown) is then used to combust the remaining synthesis gas within the low pressure gas stream 35, further increasing the temperature of the carbon dioxide containing flue gas 44 to roughly 1400° C. The carbon dioxide containing flue gas 44 is then cooled in a heat recovery train (not shown) preferably first by radiative heat transfer and then via convective heat transfer against high pressure water in a standard economizer. Enough supplemental oxygen 60 from the cryogenic air separation unit is used in the downstream section or combustion section of the OTM boiler 40 to preferably yield about 1.2 mol % excess oxygen in the carbon dioxide containing flue gas 44. Once the carbon dioxide containing flue gas 44 has cooled to sub-economizer temperatures the cooled carbon dioxide containing flue gas 44 continues to cool against low pressure boiler feed water. Due to the high moisture level in the cooled flue gas 44 some latent heat is transferable to the boiler feed water stream. In addition, some amount of energy is also available from the gasifier subsystem which optionally may be used to preheat the boiler feed water.
A cryogenic air separation unit (not shown) is used to supply gaseous oxygen to the gasifier (not shown) and the supplemental combustor operatively associated with the OTM boiler 40. This cryogenically supplied oxygen 60 accounts for roughly 33% of the total oxygen consumed by the presently disclosed process, with the other 67% supplied using the OTM elements or tubes 28, 48 in the OTM POx reactors 22, 24 and OTM boiler 40. The oxygen purity delivered by the air separation unit is preferably only about 95.5 mol % oxygen. The cryogenic air separation unit design is preferably a commercially available low purity, low pressure air separation unit, known to those persons skilled in the art cryogenic air separation plants.
The carbon dioxide containing flue gas 44 from the OTM boiler 40 is then directed to a Carbon Dioxide Processing Unit 55 or CPU. The CPU compresses and purifies the flue gas to a carbon dioxide stream 45 suitable for sequestration. Following the latent heat removal operation, the CPU compresses the carbon dioxide containing flue gas to roughly 375 psi in a five stage compression train with an average stage polytropic efficiency of about 85% and a mechanical efficiency of about 98.5%. Preferably, the compressed flue gas stream is also treated for removal of mercury, water and selected acids and preferably subjected to an auto-refrigerative process for inert removal. The auto-refrigerative process purifies the carbon dioxide stream to about 95% or greater purity with 97% recovery of carbon dioxide. This cryogenic process also produces a vent stream which is enriched in atmospheric gases (e.g., N2, O2, Ar). Following the cryogenic portion of the CPU, the purified carbon dioxide stream is further compressed to 2000 psi.
Although not shown in detail, the present advanced power cycle system 10 may also include a synthesis gas pretreatment subsystem 70 for H2S and COS control following the gasifier and before the high pressure synthesis gas flows to the first OTM POx reactor. The preferred synthesis gas pretreatment process is a warm gas cleanup process using a solid regenerable sorbent. In the preferred warm gas cleanup process, the high temperature and high pressure synthesis gas product exiting the gasifier is brought into contact with a solid metal oxide sorbent, typically ZnO such that the H2S and COS in the synthesis gas form a metal sulfide, typically ZnS. A portion of the solid sorbent is continually withdrawn from the absorber unit, regenerated and re-introduced back to the absorber unit. During the regenerating process, the spent solid sorbent is regenerated with air at near atmospheric pressure, producing ZnO and a SOx containing gas stream. The regenerated ZnO sorbent is then returned to the absorber while the SOx containing gas stream is processed for SOx control, using techniques generally known to those skilled in the art.
The key advantages and operating characteristics of the present advanced power cycle system include: (i) ability to maintain and control the membrane flux at high fuel utilizations; (ii) the OTM elements or tubes are at low pressures and the high pressure synthesis gas is contained and heated in much stronger metal tubes or heat exchangers; (iii) the flow of the synthesis gas to the multiple OTM POx stages or reactors provides an independent control variable for temperature management; (iv) design allows for standardized OTM modules which could be used in both the OTM boiler and the OTM POx reactors; (v) the use of recycled low pressure synthesis gas slip stream eliminates the need to regulate the high pressure synthesis gas exiting the gasifier or the synthesis gas pretreatment process. More importantly, the present advanced power cycle system offers process efficiency and potential cost advantages over the prior art OTM based systems used in power generation applications.
For example, because the presently disclosed advanced power cycle system and method employ a plurality of similar OTM elements or tubes placed directly within the OTM boiler as well as the OTM POx reactors where the permeated oxygen is consumed on the reactive-side of the OTM elements or tubes to produce heat, it is possible to use standardized designs the OTM elements or tubes that are similar in structure and performance. Also, because the partial oxidation and combustion reactions occurs at or on the surface of the OTM elements or tubes an extremely low oxygen partial pressure is achieved on the reactive side of the membrane elements and a driving force for oxygen ion transport from the oxidant-side to the reactant-side of the OTM elements or tubes is established since the feed air streams have a much higher oxygen partial pressure. This, in turn, allows the present advanced power cycle system to use low pressure rated OTM materials and designs while also permitting control the OTM oxygen flux with high fuel utilizations.
In addition to the aforementioned advantages and operating characteristics, the low pressure operation of the OTM elements or tubes allows for the integration of the OTM POx reactors 22, 24 and OTM boiler 40 into a single reactor housing 75 as depicted in
In the embodiment of
In the illustrated embodiment, the OTM boiler 40 is bifurcated or split into two distinct sections 40A, 40B. The first section or upstream section 40A is an OTM based section that reacts a portion of the low pressure expanded synthesis gas slip stream 27 with permeated oxygen 30 produced by the OTM elements or tubes 48 in the OTM boiler 40. The second downstream section 40B or combustion section of the OTM boiler 40 is configured to complete the combustion of any remaining low pressure synthesis gas in the slip stream 27 as well as the low pressure synthesis gas slip stream 35 through the addition of a small amount of cryogenically produced oxygen 60 into the reactor housing 75. The proposed integration of two OTM POx reactors 22, 24 and OTM boiler 40 into one integrated reactor housing 75 greatly reduces the capital cost of the overall advanced power cycle system 10. This is of course made possible by utilizing the low pressure synthesis gas slipstream 27 described above.
While the present invention has been characterized in various ways and described in relation to preferred embodiments, as will occur to those skilled in the art, numerous, additions, changes and modifications thereto can be made to the present method and system without departing from the spirit and scope of the present invention as set forth in the appended claims.
This application claims priority to and the benefit of U.S. provisional patent application Ser. No. 61/746,820 filed on Dec. 28, 2012, the disclosure of which is incorporated by reference herein.
This invention was made with Government support under Cooperative Agreement No. DE-FC26-07NT43088, awarded by the United States Department of Energy. The Government has certain rights in this invention.
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