Patent Application
20120101323
1. Field
The present embodiments generally relate to systems and methods for producing synthetic natural gas. The present embodiments relate to systems and methods for producing synthetic natural gas using low grade coal feedstocks or other carbonaceous feedstock.
2. Description of the Related Art
Clean coal technology using gasification is a promising alternative to meet the global energy demand. Most existing coal gasification processes perform best on high rank (bituminous) coals and petroleum refinery waste products but are inefficient, less reliable and expensive to operate when processing low grade coal. These low grade coal reserves including low rank and high ash coal remain underutilized as energy sources despite being available in abundance. Coal gasification coupled with methanation and carbon dioxide management offers an environmentally sound energy source. Synthetic or substitute natural gas (“SNG”) can provide a reliable supply of fuel. SNG, with the right equipment, can be produced proximate to a coal source. SNG can be transported from a production location into an already existing natural gas pipeline infrastructure, which makes the production of SNG economical in areas where it would otherwise be too expensive to mine and transport low grade coal. Alternatively, in developing countries, the production and supply of clean efficient SNG to densely populated cities instead of the transport and use of low grade coal as an energy source in a multitude of inefficient and polluting facilities within the cities provides the means to effectively mitigate pollutants and carbon capture.
A typical problem with SNG generation is the high auxiliary power and process water requirements. Often a large quantity of outside power is required to run a SNG production system, and a large quantity of water needs to be supplied to the SNG production system to accommodate the processes of the system. The large quantities of water and outside power needed to run the SNG production system can greatly escalate the cost of production and limit where SNG generation systems can be deployed.
A need exists, therefore, for more efficient systems and methods for producing SNG from coal that reduce the requirements for outside power and water.
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
A detailed description will now be provided. Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the “invention” may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the “invention” will refer to subject matter recited in one or more, but not necessarily all, of the claims. Each of the inventions will now be described in greater detail below, including specific embodiments, versions and examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the inventions, when the information in this patent is combined with available information and technology.
Systems and methods for producing synthetic natural gas are provided. The method can include gasifying a carbonaceous feedstock within a gasifier to provide a raw syngas. The raw syngas can be cooled to provide a cooled raw syngas. The cooled raw syngas can be processed in a purification system to provide treated syngas. The purification system can include a flash gas separator in fluid communication with the gasifier and a saturator. The treated syngas can be converted to synthetic natural gas to provide steam, a methanation condensate, and a synthetic natural gas. The methanation condensate can be introduced to the flash gas separator.
In one or more embodiments, the raw syngas via line 106 can be cooled using a heat transfer medium introduced via line 108 and/or line 112. Although not shown, in a non-limiting embodiment, the heat transfer medium in line 108 and/or 112 can include process steam or condensate from the syngas purification systems 400. The heat transfer medium can be process water, boiler feed water, superheated low pressure steam, superheated medium pressure steam, superheated high pressure steam, saturated low pressure steam, saturated medium pressure steam, saturated high pressure steam, and the like. Heat from the raw syngas introduced via line 106 to the syngas cooler 305 can be indirectly transferred to the heat transfer medium introduced via line 108 and/or 112. For example, heat from the raw syngas introduced via line 106 to the syngas cooler 305 can be indirectly transferred to boiler feed water introduced via line 108 and/or 112 to provide superheated high pressure steam via line 110 and/or line 114. In one or more embodiments, the cooled syngas via line 116 can be introduced to the purification system 400 to provide a purified syngas via line 118.
In one or more embodiments, the purified syngas via line 118 and a heat transfer medium via line 120 can be introduced to the methanator 500 to provide a methanated syngas or SNG via line 122 and steam via line 124. The methanation of the purified syngas is an exothermic reaction that generates heat. The heat generated during methanation of the purified syngas can be indirectly transferred to the heat transfer medium introduced via line 120 to provide the steam via line 124. In one or more embodiments, lines 124, 112 can include process condensate, methanation condensate, steam, and/or a combination thereof.
The heat transfer medium in line 120 can be process water, boiler feed water, and the like. For example, boiler feed water introduced via line 120 to the methanator 500 can be heated to provide low pressure steam, medium pressure steam, high pressure steam, saturated low pressure steam, saturated medium pressure steam, or saturated high pressure steam. In one or more embodiments, at least a portion of the steam in line 124 can be introduced to the syngas cooler 305 as the heat transfer medium introduced via line 112. In one or more embodiments, another portion of the steam via line 124 can be provided to various process units within SNG generation system 100 (not shown). In one or more embodiments, the steam in line 124 can have a temperature of about 250° C. or more, about 350° C. or more, about 450° C. or more, about 550° C. or more, about 650° C. or more, or about 750° C. or more. In one or more embodiments, the steam in line 124 can be at a pressure of about 4,000 kPa or more, about 7,500 kPa or more, about 9,500 kPa or more, about 11, 500 kPa or more, about 14,000 kPa or more, about 16,500 kPa or more, about 18,500 kPa or more, about 20,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more. For example, the steam in line 124 can be at a pressure of from about 4,000 kPa to about 14,000 kPa or from about 7,000 kPa to about 10,000 kPa.
In one or more embodiments, the steam in line 112 can be further heated within the syngas cooler 305 to provide superheated high pressure steam or steam at a higher temperature and/or pressure than in line 112 via line 114. In one or more embodiments, the heat transfer medium, for example boiler feed water, introduced via line 108 to the syngas cooler 305 can be heated to provide superheated high pressure steam via line 110. The steam via line 110 and/or line 114 can have a temperature of about 450° C. or more, about 550° C. or more, about 650° C. or more, or about 750° C. or more. The steam via line 110 and/or line 114 can have a pressure of about 4,000 kPa or more, 8,000 kPa or more, about 11,000 kPa or more, about 15,000 kPa or more, about 17,000 kPa or more, about 19,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more.
Although not shown, in one or more embodiments, the steam in line 112 can be introduced or otherwise mixed with the heat transfer medium in line 108 to provide a heat transfer medium mixture or “mixture.” In one or more embodiments, the mixture can be introduced as the heat transfer medium to the syngas cooler 305 to provide the superheated high pressure steam via line 110 and/or line 114. In one or more embodiments, the mixture can be recovered from the syngas cooler 305 via a single line (not shown).
In one or more embodiments, at least a portion of the superheated high pressure steam via lines 110 and/or line 114 can be used to generate auxiliary power for the SNG system 100. In one or more embodiments, at least a portion of the superheated high pressure steam via lines 110 and/or line 114 can be introduced to the gasifier 205. For example, the superheated high pressure steam via lines 110 and/or line 114 can be introduced to the gasifier 205 after pressure let down, for example from a steam turbine.
In one or more embodiments, the syngas purification system 400 can remove particulates, ammonia, carbonyl sulfide, chlorides, mercury, and/or acid gases. In one or more embodiments, the syngas purification system 400 can saturate the cooled syngas with water, shift convert carbon monoxide to carbon dioxide, or combinations thereof.
In one or more embodiments, the treated syngas in line 118 can include, but is not limited to, hydrogen, carbon monoxide, carbon dioxide, methane, nitrogen, argon, or any combination thereof. In one or more embodiments, the treated syngas in line 118 can have a hydrogen content ranging from a low of about 10 mol % to a high of about 80 mol %. In one or more embodiments, the treated syngas in line 118 can have a carbon monoxide content ranging from a low of about 0 mol % to a high of about 30 mol %. In one or more embodiments, the treated syngas in line 118 can have a carbon dioxide content ranging from a low of about 0 mol % to a high of about 40 mol %. In one or more embodiments, the treated syngas in line 118 can have a methane content ranging from about 0 mol % to about 30 mol %. In one or more embodiments, the treated syngas in line 118 can have a methane content ranging from a low of about 1 mol %, about 3 mol %, about 4.5 mol %, or about 3 mol % to a high of about 8 mol %, about 8.5 mol %, about 9 mol %, or about 9.5 mol % or more. In one or more embodiments, the treated syngas in line 118 can have a nitrogen content ranging from a low of about 0 mol % to a high of about 50 mol %. In one or more embodiments, the treated syngas in line 118 can have an argon content ranging from a low of about 0 mol % to a high of about 5 mol %. The low inert concentration, e.g. the low concentration of nitrogen and argon in the treated syngas via line 118 can increase the heating value of the SNG provided via line 122 from the methanator 300.
A higher methane concentration in the treated syngas via line 118 can be beneficial thr SNG production, and can provide a product value, for example a heating value, and can also reduce the product gas recycle requirements to quench the heat of reaction within the methanator 500. The methane concentration can also reduce auxiliary power consumption, capital costs, and operating costs of the SNG system.
In one or more embodiments, the treated syngas via line 118 can be introduced to the methanator 500 to provide SNG via line 122. The methanator 500 can be or include any device, system, or combinations of systems and/or devices suitable for converting at least a portion of the hydrogen and carbon monoxide and/or carbon dioxide to SNG. In one or more embodiments, the SNG in line 122 can have a methane content ranging from a low of about 0.01 mol % to a high of 100 mol %. For example, the SNG in line 122 can have a methane content ranging from a low of about 65 mol %, about 75 mol %, or about 85 mol % to a high of about 90 mol %, about 95 mol %, or about 100 mol %. In one or more embodiments, the methanator 500 can be operated at a temperature ranging from a low of about 150° C., about 425° C., about 450° C., or about 473° C. to a high of about 535° C., about 565° C., or about 590° C. In one or more embodiments, the methanator 500 can be operated at a temperature ranging from a low of about 590° C., about 620° C., or about 640° C. to a high of about 660° C., about 675° C. about 700° C., or about 1,000° C.
Feedstock via line 102, steam via line 127 and an oxidant via line 104 can be combined in the mixing zone 215 to provide a gas mixture. The feedstock via line 102 can include any suitable carbonaceous material. The carbonaceous material can include, but is not limited to, one or more carbon-containing materials whether solid, liquid, gas, or a combination thereof. The one or more carbon-containing materials can include but are not limited to coal, coke, petroleum coke, cracked residue, whole crude oil, crude oil, vacuum gas oil, heavy gas oil, residuum, atmospheric tower bottoms, vacuum tower bottoms, distillates, paraffins, aromatic rich material from solvent deasphalting units, aromatic hydrocarbons, asphaltenes, naphthenes, oil shales, oil sands, tars, bitumens, kerogen, waste oils, biomass (e.g., plant and/or animal matter or plant and/or animal derived matter), tar, low ash or no ash polymers, hydrocarbon-based polymeric materials, heavy hydrocarbon sludge and bottoms products from petroleum refineries and petrochemical plants such as hydrocarbon waxes, byproducts derived from manufacturing operations, discarded consumer products, such as carpet and/or plastic automotive parts/components including bumpers and dashboards, recycled plastics such as polypropylene, polyethylene, polystyrene, polyurethane, derivatives thereof, blends thereof, or any combination thereof. Accordingly, the process can be useful for accommodating mandates for proper disposal of previously manufactured materials.
In one or more embodiments, the coal can include, but is not limited to high-sodium and/or low-sodium lignite, subbituminous, bituminous, anthracite, or any combination thereof. The hydrocarbon-based polymeric materials can include, for example, thermoplastics, elastomers, rubbers, including polypropylenes, polyethylenes, polystyrenes, including other polyolefins, polyurethane, homo polymers, copolymers, block copolymers, and blends thereof; polyethylene terephthalate (PET), poly blends, other polyolefins, poly-hydrocarbons containing oxygen, derivatives thereof, blends thereof, and combinations thereof.
In one or more embodiments, depending on the moisture concentration of the carbonaceous material, for example coal, the carbonaceous material can be dried prior to introduction to the gasifier 205. The carbonaceous material can be pulverized by milling units such as one or more bowl mills and heated to provide a carbonaceous material containing a reduced amount of moisture. For example, the carbonaceous material can be dried to provide a carbonaceous material containing less than about 50% moisture, less than about 30% moisture, less than about 20% moisture, less than about 15% moisture, or less. The carbonaceous material can be dried directly in the presence of a gas, for example nitrogen or indirectly using any heat transfer medium via coils, plates or other heat transfer equipment.
The oxidant introduced via line 104 can include, but is not limited to, air, oxygen, essentially oxygen, oxygen-enriched air, mixtures of oxygen and air, mixtures of oxygen and inert gas such as nitrogen and argon, and combinations thereof. As used herein, the term “essentially oxygen” refers to an oxygen feed containing 51% vol oxygen or more. As used herein, the term “oxygen-enriched air” refers to air containing greater than 21% vol oxygen. Oxygen-enriched air can be obtained, for example, from cryogenic distillation of air, pressure swing adsorption, membrane separation, or any combination thereof. In one or more embodiments, the oxidant introduced via line 104 can be nitrogen-free or essentially nitrogen-free. By “essentially nitrogen-free,” it is meant that the oxidant in line 104 contains less than about 5% vol nitrogen, less than about 4% vol nitrogen, less than about 3% vol nitrogen, less than about 2% vol nitrogen, or less than about 1% vol nitrogen. In one or more embodiments, the steam via line 127 can be any suitable type of steam, for example low pressure steam, medium pressure steam, high pressure steam, superheated low pressure steam, superheated medium pressure steam, or superheated high pressure steam.
The amount of oxidant introduced via line 104 to the mixing zone 215 can range from about 1% to about 90% of the stoichiometric oxygen required to oxidize the total amount of carbonaceous materials in the carbonaceous solids and/or the carbonaceous containing solids. The oxygen concentration within the gasifier 205 can range from a low of about 1%, about 3%, about 5%, or about 7% to a high of about 30%, about 40%, about 50%, or about 60% of the stoichiometric requirements based on the molar concentration of carbon in the gasifier 205. In one or more embodiments, the oxygen concentration within the gasifier 205 can range from a low of about 0.5%, about 2%, about 6%, or about 10%, to a high of about 60%, about 70%, about 80%, or about 90% of the stoichiometric requirements based on the molar concentration of carbon in the gasifier 205.
In one or more embodiments, the carbon containing feedstock introduced via line 102 can have nitrogen containing compounds. For example, the feedstock via line 102 can be coal or petroleum coke that contains about 0.5 mol %, about 1 mol %, about 1.5 mol %, about 2 mol % or more nitrogen in the feedstock based on ultimate analysis of the carbonaceous material. In one or more embodiments, at least a portion of the nitrogen contained in the feedstock introduced via line 102 can be converted to ammonia within the gasifier 205. In one or more embodiments, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80% or more of the nitrogen in the feedstock can be converted to ammonia within the gasifier 205. For example, the amount of nitrogen in the feedstock converted within the gasifier 205 to ammonia can range from a low of about 20%, about 25%, about 30%, or about 35% to a high of about 70%, about 80%, about 90%, or about 100%. In one or more embodiments, steam via line 127 can be introduced to the mixing zone 215. The steam and oxidant can be introduced separately, as shown, to the mixing zone 215 or mixed prior to introduction to the mixing zone (not shown). The feedstock, steam, and oxidant can be introduced sequentially into the gasifier 205. The feedstock, steam, and oxidant can be introduced simultaneously into the gasifier 205. In one or more embodiments, steam can be mixed with the feedstock, oxidant, or both. Feed (i.e. introduction of the feedstock, steam, and oxidant) to the gasifier 205 can be continuous or intermittent depending on desired product types and grades of the raw syngas. The one or more oxidants can be introduced at the bottom of the mixing zone 215 to increase the temperature within the mixing zone 215 and riser 220 by combusting at least a portion of any carbon contained within particulates recirculated via line 255.
The gasifier 205 can be operated at a temperature range sufficient as to not melt the ash or to provide a molten ash or slag, such as from about 550° C. to about 2,050° C., from about 275° C. to about 950° C., or from about 1,000° C. to about 1,150° C. Heat can be supplied by burning the carbon in the recirculated solids in a lower portion of the mixing zone 215 before recirculated solids contact the entering feedstock. Startup can be initiated by bringing the mixing zone 215 to a temperature from about 500° C. to about 650° C. and optionally by feeding coke breeze or the equivalent to the mixing zone 215 to further increase the temperature of the mixing zone 215 to about 900° C. In one or more embodiments, the gasifier 205 can have a temperature of about 870° C. to about 1,100° C., about 890° C. to about 940° C., or about 880° C. to about 1,050°.
The operating temperature of the gasifier 205 can be controlled by the recirculation rate and residence time of the solids within the riser 220; by reducing the temperature of the ash prior to recycle via line 255 to the mixing zone 215; by the addition of steam to the mixing zone 215; and/or by varying the amount of oxidant added to the mixing zone 215. The recirculating solids introduced via line 255 can serve to rapidly heat the incoming feedstock, which also can mitigate tar formation.
The residence time and temperature in the mixing zone 215 and the riser 220 can be sufficient for water-gas shift reaction to reach near equilibrium conditions and to allow sufficient time for tar cracking. The residence time of the feedstock in the mixing zone 215 and riser 220 can be greater than about 2 seconds. The residence time of the feedstock in the mixing zone 215 and riser 220 can be greater than about 5 seconds. The residence time of the feedstock in the mixing zone 215 and riser 220 can be greater than about 10 seconds.
In one or more embodiments, the mixing zone 215 can be operated at pressures from about 100 kPa to about 6,000 kPa to increase thermal output per unit reactor cross-sectional area and enhance raw syngas energy output. In one or more embodiments, the mixing zone 215 can be operated at a pressure ranging from a low of about 600 kPa, about 650 kPa, or about 700 kPa to a high of about 2,250 kPa, about 3,250 kPa, or about 3,950 kPa or more. In one or more embodiments, the mixing zone 215 can be operated at a temperature ranging from a low of about 250° C., about 400° C., or about 500° C. to a high of about 650° C., about 800° C., or about 1,000° C. In one or more embodiments, the mixing zone 215 can be operated at a temperature of from about 350° C. to about 950° C., from about 475° C. to about 900° C., from about 899° C. to about 927° C., or from about 650° C. to about 875° C.
The gas mixture can flow through the mixing zone 215 into the riser 220 where additional residence time allows the gasification, steam/methane reforming, tar cracking, and/or water-gas shift reactions to occur. In one or more embodiments, the riser 220 can operate at a higher temperature than the mixing zone 215. In one or more embodiments, the riser 220 can have a smaller diameter or cross-sectional area than the mixing zone 215. In one or more embodiments, the riser 220 can have the same diameter or cross-sectional area as the mixing zone 215. The superficial gas velocity in the riser 220 can range from about 3 m/s to about 27 m/s, from about 6 m/s to about 24 m/s, from about 9 m/s to about 21 m/s, or from about 9 m/s to about 12 m/s, or from about 11 m/s to about 18 m/s. Suitable temperatures in the riser 220 can range from about 550° C. to about 2,100° C. For example, suitable temperatures within the riser 220 can range from a low of about 700° C., about 800° C., about 900° C., to a high of about 1050° C. about 1150° C., about 1250° C., or more.
The gas mixture can exit the riser 220 and enter the disengagers 230, 240 where at least a portion of particulates can be separated from the gas and recycled back to the mixing zone 215 via one or more conduits, including, but not limited to, a standpipe 250, and/or j-leg 255. The j-leg 255 can include a non-mechanical “j-valve,” “L-valve,” or other valve to increase the effective solids residence time, increase the carbon conversion, and minimize aeration requirements for recycling solids to the mixing zone 215. The disengagers 230, 240 can be cyclones. One or more particulate transfer devices 245, such as one or more loop seals, can be located downstream of the disengagers 230, 240 to collect separated particulates. At least a portion of any entrained or residual particulates in the raw syngas via line 106 can be removed using the one or more particulate removal systems (not shown).
In one or more embodiments, the raw syngas in line 106 can include, but is not limited to, hydrogen, carbon monoxide, carbon dioxide, methane, nitrogen, argon, or any combination thereof. In one or more embodiments, the raw syngas in line 106 can have a hydrogen content ranging from a low of about 40 mol % to a high of about 80 mol %. In one or more embodiments, the raw syngas in line 106 can have a carbon monoxide content ranging from a low of about 15 mol % to a high of about 25 mol %. In one or more embodiments, the raw syngas in line 106 can have a carbon dioxide content ranging from a low of about 0 mol % to about 40 mol %. In one or more embodiments, the raw syngas in line 106 can be have a methane content ranging from a low of about 0 mol %, about 5 mol %, or about 10 mol % to a high of about 20 mol %, about 30 mol %, or about 40 mol %. In one or more embodiments, the raw syngas in line 106 can have a methane content ranging from a low of about 3.5 mol %, about 4 mol %, about 4.5 mol %, or about 5 mol % to a high of about 8 mol %, about 8.5 mol %, about 9 mol %, or about 9.5 mol % or more. In one or more embodiments, the raw syngas in line 106 can have a nitrogen content ranging from a low of about 0 mol %. 1 mol %, or 2 mol % to a high of about 3 mol %, about 6 mol %, or about 10 mol %. In one or more embodiments, when air or excess air is introduced as an oxidant via line 104 to the gasifier 205, the nitrogen content in raw syngas in line 106 can range from about 10 mol % to about 50 mol % or more. In one or more embodiments, when an essentially nitrogen free oxidant is introduced via line 104 to the gasifier 205, the nitrogen content in the raw syngas in line 106 can range from about 0 mol % to about 4 mol %. In one or more embodiments, the raw syngas in line 106 can have an argon content ranging from a low of about 0 mol %, 0.5 mol %, or 1 mol % to a high of about 1.5 mol %, about 2 mol %, or about 3 mol %. In one or more embodiments, an essentially nitrogen free oxidant introduced via line 104 can provide raw syngas via line 106 having a combined nitrogen and argon concentration ranging from a low of about 0.001 mol % to a high of about 3 mol %.
The average particle diameter size of the feedstock via line 102 can be used as a control variable to optimize particulate density of the solids recycled to the mixing zone via the standpipe 250. The particle size of the feedstock introduced via line 102 can be varied to optimize the particulate mass circulation rate, and to improve the flow characteristics of the gas-solid mixture within the mixing zone 215 and riser 220. Steam via line 127 can be supplied to the gasifier 205 both as a reactant and as a moderator to control the reaction temperature.
In one or more embodiments, one or more sorbents can be introduced to the gasifier 205. The one or more sorbents can capture contaminants from the syngas, such as sodium vapor in the gas phase within the gasifier 205. The one or more sorbents can scavenge oxygen at a rate and level sufficient to delay or prevent oxygen from reaching a concentration that can result in undesirable side reactions with hydrogen (e.g. water) from the feedstock within the gasifier 205. The one or more sorbents can be mixed or otherwise added to the one or more feedstocks. The one or more sorbents can be used to dust or coat feedstock particles in the gasifier 205 to reduce the tendency for the particles to agglomerate. The one or more sorbents can be ground to an average particle size of about 5 microns to about 100 microns, or about 10 microns to about 75 microns. Illustrative sorbents can include but are not limited to, carbon rich ash, limestone, dolomite, kaolin, silica flour, and coke breeze. Residual sulfur released from the feedstock can be captured by native calcium in the feed or by a calcium-based sorbent to form calcium sulfide.
The syngas cooler 305 can include one or more heat exchangers or heat exchanging zones. As illustrated the syngas cooler 305 can include three heat exchanger zones 310, 320, and 330. The heat exchanging zones 310, 320, and 330 can be arranged in series. The raw syngas via line 106 can be cooled by indirect heat exchange in the first heat exchanger (“first Lone”) 310 to a temperature of from about 260° C. to about 820° C. The cooled raw syngas exiting the first heat exchanger 310 via line 315 can be further cooled by indirect heat exchange in the second heat exchanger (“second zone”) 320 to a temperature of from about 260° C. to about 704° C. The cooled raw syngas exiting the second heat exchanger 320 via line 325 can be further cooled by indirect heat exchange in the third heat exchanger (“third zone”) 330 to a temperature of from about 260° C. to about 430° C. Although not shown, the syngas cooler 305 can be or include a single boiler, for example.
The raw syngas via line 106 can be cooled by indirectly transferring heat from the raw syngas to a heat transfer medium within the syngas cooler 305. In one or more embodiments, the heat transfer medium via line 108 can be introduced to the syngas cooler 305. The heat transfer medium via line 108 can be process water, boiler feed water, or the like. Heat from the raw syngas can be indirectly transferred to the heat transfer medium introduced via line 108 to provide superheated steam or superheated high pressure steam which can be recovered via line 350. The superheated steam or superheated high pressure steam via line 350 can be used to power one or more steam turbines 360, which can be coupled to an electric generator 380. The condensate recovered via line 390 from the steam turbine 360 can be recycled to the heat transfer medium in line 108. For example, the condensate recovered via line 390 from steam turbine 360 can be treated and recycled to provide at least a portion of the heat transfer medium in line 108.
Boiler feed water, for example, via line 108 can be heated within the third heat exchanger (“economizer”) 330 to provide the cooled syngas via line 116 and a condensate via line 338. The condensate via line 338 can be saturated or substantially saturated at the process conditions. The condensate 338 can be introduced (“flashed”) to one or more steam drums or separators 340 to separate the gas phase (“steam”) from the liquid phase (“condensate”). Steam via line 342 can be introduced to the second heat exchanger (“superheater”) 320 and heated against the incoming syngas via line 315 to provide the superheated steam or superheated high pressure steam via line 350.
The superheated steam or superheated high pressure steam via line 350 from the syngas cooler 305 can have a temperature of about 400° C. or more, about 450° C. or more about 500° C. or more, about 550° C. or more, about 600° C. or more, about 650° C. or more, about 700° C. or more, or about 750° C. or more. The superheated steam or superheated high pressure steam via line 350 can have a pressure of about 4,000 kPa or more, 8,000 kPa or more, about 11,000 kPa or more, about 15,000 kPa or more, about 17,000 kPa or more, about 19,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more.
The condensate via line 346 from the separator 340 can be introduced to the first heat exchanger (“boiler”) 310 and indirectly heated against the svngas introduced via line 106 to provide at least partially vaporized steam which can be introduced to the separator 340 via line 344. The steam returned via line 344 to the separator 340 can be introduced via line 342 for superheating in the second heat exchanger 320 to provide the superheated steam or superheated high pressure steam via line 350 for use in the one or more steam turbines 360.
Any one or all of the heat exchangers 310, 320, 330 can be shell-and-tube type heat exchangers. The raw syngas in line 106 can be supplied in series to the shell-side or tube-side of the first heat exchanger 310, second heat exchanger 320, and third heat exchanger 330. The heat transfer medium can pass through either the shell-side or tube-side, depending on which side the raw syngas is introduced. In one or more embodiments, the raw syngas in line 106 can be supplied in parallel (not shown) to the shell-side or the tube-side of the first heat exchanger 310, second heat exchanger 320, and third heat exchanger 330 and the heat transfer medium can pass serially through either the shell-side or tube-side, depending on which side the raw syngas is introduced.
As discussed and described above with reference to
In one or more embodiments, the air separation unit 222 can supply oxygen at a pressure ranging from about 2,000 kPa to 10,000 kPa or more. For example, the air separation unit 222 can supply oxygen of about 99.5 percent purity at a pressure of about 1,000 kPa greater than the pressure within the gasifier 205 and ambient temperature to the gasifier 205. The flow of oxygen can be controlled to limit the amount of carbon combustion that takes place within the gasifier 205 and to maintain gasifier temperature. The oxygen can enter the gasifier 205 at a ratio (weight of oxygen to weight of feedstock on a dry and mineral matter free basis) ranging from about 0.1:1 to about 1.2:1. In one or more embodiments, the ratio of oxygen to the feedstock can be about 0.66:1 to about 0.75:1.
As discussed and described above with reference to
The syngas in line 106 can be cooled by the syngas cooler 305, and the cooled syngas via line 116 can be introduced to the syngas purification system 400. In one or more embodiments, the syngas purification system 400 can include one or more particulate control devices 410, one or more saturators 420, one or more gas shift devices 430, one or more COS hydrolysis devices 480, one or more ammonia scrubbing devices 490, one or more gas coolers 440, one or more flash gas separators 446, one or more mercury removal devices 450, one or more acid gas removal devices 460, one or more sulfur recovery units 466, and/or one or more carbon handling compression units 470.
The cooled syngas can be introduced via line 116 to the particulate control device 410. The particulate control device 410 can include one or more separation devices such as high temperature particulate filters. The particulate control device 410 can provide a filtered syngas with a particulate concentration below the detectable limit of about 0.1 ppmw. An illustrative particulate control device can include, but is not limited to sintered metal filters (for example, iron aluminide filter material), metal filter candles, and/or ceramic filter candles. The particulate control device 410 can eliminate the need for a water scrubber, due to the efficacy of removing particulates from the syngas. The elimination of a water scrubber can allow for the elimination of dirty water or grey water systems, which can reduce the process water consumption and associated waste water discharge.
The solid particulates can be purged from the system via line 412, or recycled to the gasifier 205 (not shown). The filtered syngas via line 414 leaving the particulate control device 410 can be divided and at least a portion of the syngas can be introduced to the saturator 420 via line 415, and another portion can introduced via line 416 to the carbonyl sulfide (“COS”) hydrolysis device 480. Heat can be recovered from the cooled syngas in line 416. For example, the cooled syngas in line 416 can be exposed to a heat exchanger or a series of heat exchangers (not shown). In one or more embodiments, the portion of cooled syngas introduced to the saturator 420 via line 415 and the portion provided to the COS hydrolysis device 480 via line 416 can be based, at least in past, on the desired ratio of hydrogen to carbon monoxide and/or carbon dioxide at the inlet of the methanation device 500. Although not shown, in one or more embodiments the filtered syngas via line 414 can be introduced serially to both the saturator 420 and the COS hydrolysis device 480.
The saturator 420 can be used to increase the moisture content of the cooled syngas in line 415, before the cooled syngas is introduced via line 424 to the gas shift device 430. Process condensate generated by other devices in the SNG system 300 can be introduced via line 442 to the saturator 420. Illustrative condensates can include process condensate from the ammonia scrubber 490, a first process condensate from the syngas cooler 305, a second process condensate from the gas cooler 440, a process condensate from methanator 500, or a combination thereof. Make-up water, such as demineralized water, can also be supplied via line 418 to the saturator 420. The make-up water can be used to maintain a proper water balance.
In one or more embodiments, the saturator 420 can have a heat requirement, and about 70 percent to 75 percent of the heat requirement can be sensible heat provided by the cooled syngas in line 415, as well as medium to low grade heat available from other portions of the SNG system 300. About 25 percent to 30 percent of the heat requirement can be supplied by indirect steam reboiling. In one or more embodiments, the indirect steam reboiling can use medium pressure steam, for example the steam can have a pressure ranging from about 4,000 kPa to about 4,580 kPa. In one or more embodiments, the saturator 420 does not have a live steam addition. The absence of live steam addition to the saturator 420 can minimize the overall required water make-up and reduce saturator blow down via line 422.
Saturated syngas can be introduced via line 424 to the gas shift device 430. In one or more embodiments, the gas shift device 430 can include a system of parallel single-stage or two-stage gas shift catalytic beds. The saturated syngas in line 424 can be preheated before entering the gas shift device 430. The saturated syngas can enter the gas shift device 430 with a steam-to-dry gas molar ratio ranging from about 0.8:1 to about 1.2:1 or higher. The temperature of the saturated syngas in line 424 can range from about 200° C. to about 295° C., from about 190° C. to about 290° C., or from about 290° C. to about 300° C. or more. The saturated syngas in line 424 can include carbonyl sulfide, which can be at least partially hydrolyzed to hydrogen sulfide by the gas shift device 430.
The gas shift device 430 can be used to convert the saturated syngas to provide a shifted syngas via line 432. In one or more embodiments, the gas shift device 430 can include one or more shift converters to adjust the hydrogen to carbon monoxide ratio of the syngas by converting carbon monoxide to carbon dioxide. The gas shift device 430 can include, but is not limited to, single stage adiabatic fixed bed reactors; multiple-stage adiabatic fixed bed reactors with interstage cooling, steam generation or cold quench reactors; tubular fixed bed reactors with steam generation or cooling; fluidized bed reactors, or any combination thereof.
In one or more embodiments, a cobalt-molybdenum catalyst can be incorporated into the gas shift device 430. The cobalt-molybdenum catalyst can operate at a temperature of about 290° C. in the presence of hydrogen sulfide, such as about 100 ppmw hydrogen sulfide. If the cobalt-molybdenum catalyst is used to perform a sour shift, subsequent downstream removal of sulfur can be accomplished using any sulfur removal method and/or technique.
The gas shift device 430 can include two reactors arranged in series. A first reactor can be operated at high temperature of from about 260° C. to about 400° C. to convert a majority of the carbon monoxide present in the saturated syngas in line 424 to carbon dioxide at a relatively high reaction rate using a catalyst which can be, but is not limited to copper-zinc-aluminum, iron oxide, zinc ferrite, magnetite, chromium oxides, derivatives thereof, or any combination thereof. A second reactor can be operated at a relatively low temperature of about 150° C. to about 200° C. to maximize the conversion of carbon monoxide to carbon dioxide and hydrogen. The second reactor can use a catalyst that includes, but is not limited to copper, zinc, copper promoted chromium, derivatives thereof, or any combination thereof. The gas shift device 430 can recover heat from the shifted syngas. The recovered heat can be used to preheat the saturated syngas in line 424 before it enters the gas shift device 430. In one or more embodiments the recovered heat can provide at least a portion of the heat duty for the svngas saturator 420. In one or more embodiments, the recovered heat can pre-heat feed gas to the shift reactors and/or produce medium pressure steam. In one or more embodiments, the recovered heat can pre-heat recycled condensate or preheat make-up water introduced to the SNG system 300. In one or more embodiments, the recovered heat can provide at least a portion of the heat duty for the acid gas removal device 460. In one or more embodiments, the recovered heat can provide at least a portion of the heat to dry the carbonaceous feedstock and/or other systems within the SNG system 300.
After the saturated syngas is shifted forming a shifted syngas, the shifted syngas can be introduced via line 432 to a gas cooler 440. The gas cooler 440 can be an indirect heat exchanger. The gas cooler 440 can recover at least a portion of heat from the shifted syngas in line 432 not recovered by the gas shift device 430. The gas cooler 440 can produce cooled shift converted syngas and a second condensate. The cooled shift converted syngas can leave the gas cooler 440 via line 449. The second process condensate from 440 can be introduced via line 442 to the saturator 420 after passing through the flash gas separator 446.
The COS hydrolysis device 480 can convert carbonyl sulfide in the cooled syngas in line 416, to hydrogen sulfide. The COS hydrolysis device 480 can include a number of parallel carbonyl sulfide reactors. For example, the COS hydrolysis device 480 can have about two or more, three or more, four or more, five or more, or ten or more parallel carbonyl sulfide reactors. The filtered syngas in line 416 can enter the COS hydrolysis device 480, pass over the parallel carbonyl sulfide reactors, and hydrogen sulfide syngas can exit the COS hydrolysis device 480 via line 482. The hydrogen sulfide syngas in line 482 can have a carbonyl sulfide concentration of about 1 ppmv or less. The heat in the hydrogen sulfide syngas in line 482 can be recovered and used to preheat boiler feedwater, to dry the carbonaceous feedstock, as a heat source in other portions of the SNG system 300, or any combination thereof. A heat exchanger (not shown) can be used to recover the heat from the hydrogen sulfide syngas in line 482; illustrative heat exchangers can include a shell and tube heat exchanger, a concentric flow heat exchanger, or any other heat exchanging device. After the heat is recovered from the hydrogen sulfide syngas in line 482, the hydrogen sulfide syngas in line 482 can be introduced to the ammonia scrubbing device 490.
The ammonia scrubbing device 490 can use water to remove ammonia from the hydrogen sulfide syngas in line 482. Water via line 488 can be introduced to the ammonia scrubber 490. The water via line 488 can be recycle water from other parts of the SNG generation system 300 or can be make-up water supplied from an external source. In one or more embodiments, the water supplied to the ammonia scrubber 490 via line 488 can include water produced during the drying of the carbonaceous feedstock. The water via line 488 used to scrub the cooled syngas can be provided at a temperature ranging from about 50° C. to about 64° C. In one or more embodiments, the water can have a temperature of about 54° C. The water can also remove at least a portion of any fluorides and/or chlorides in the syngas. Accordingly, waste water having ammonia, fluorides, and/or chlorides can be provided by the ammonia scrubber, and the waste water from the ammonia scrubber 490 can be introduced via line 492 to the gas cooler 440 and combined with the second process condensate to provide a combined condensate. The combined condensate can be provided via line 444 to flash gas separator 446, any flash gas separator can be used. The combined condensate in line 444 can be pre-heated before entering the flash gas separator 446. The combined condensate in line 444 can have a pressure ranging from about 2,548 kPa to about 5,922 kPa. The combined condensate in line 444 can be flashed in the flash gas separator 446. When the combined condensate is flashed a flashed gas and a condensate can be formed. The flashed gas can include ammonia. The flashed gas can be recycled back to the gasifier 205 via line 448. The condensate can be recycled to the saturator 420, via line 442. In one or more embodiments, the ammonia in the flashed gas in line 448 can be converted within the gasifier 205 to nitrogen and hydrogen.
Scrubbed syngas can be introduced to the gasifier 205 from the ammonia scrubber 490 via line 494. In one or more embodiments, a portion of the scrubbed syngas in line 494 can be recycled back to the gasifier 205 via line 496. In one or more embodiments, another portion of the scrubbed syngas in line 494 can be combined with the cooled shifted syngas in line 449 to provide a mixed syngas via line 497. The mixed syngas in line 497 can be pre-heated and introduced to the mercury removal device 450. The mixed syngas in line 497 can have a temperature ranging from about 60° C. to about 71° C., from about 20° C. to 80° C., or from about 60° C. to about 90° C.
The mercury removal device 450 can include, but is not limited to, activated carbon beds that can adsorb a substantial amount, if not all, of the mercury present in the processed syngas. The processed syngas recovered via line 452 from the mercury removal device 450 can be introduced to the acid gas removal device 460.
The acid gas removal device 460 can remove carbon dioxide from the processed syngas. The acid gas removal device 460 can include, but is not limited to a physical solvent based two stage acid gas removal system. The physical solvents can include, but are not limited to Selexol™ (dimethyl ethers of polyethylene glycol) Rectisol® (cold methanol), or combinations thereof. In one or more embodiments, one or more amine solvents such as methyl-diethanolamine (MDEA) can be used to remove at least a portion of any acid gas from the processed syngas to provide a treated syngas via line 118. The treated syngas can be introduced via line 118 to the methanator 500. The treated syngas in line 118 can have a carbon dioxide content from about 0 mol % to a high of about 40 mol %. The treated syngas in line 118 can have a total sulfur content of about 0.1 ppmv or less.
The carbon dioxide can be recovered as a low-pressure carbon dioxide rich stream via line 464. The carbon dioxide content in line 464 can be about 95 mol % carbon dioxide or more. The low-pressure carbon dioxide stream can have a hydrogen sulfide content of less than 20 ppmv. The low-pressure carbon dioxide stream can be introduced via line 464 to the carbon handling compression unit 470. The low-pressure carbon dioxide stream in line 464 can be exposed to one or more compression trains and the carbon dioxide can leave the carbon handling compression unit 470 via line 472 as a dense-phase fluid at a pressure ranging from about 13,890 kPa to about 22,165 kPa. In one or more embodiments, the dense-phase fluid can be used for enhanced oil recovery or sequestered. In one or more embodiments, the carbon handling compression unit 470 can be a four stage compressor or any other compressor. An illustrative compressor can include a four stage intercooled centrifugal compressor with electric drives. In one or more embodiments, the carbon dioxide stream in line 472 can conform to carbon dioxide pipeline specifications.
The acid gas removal device 460 can also remove sulfur from the processed gas. The sulfur can be concentrated as a hydrogen sulfide rich stream. The hydrogen sulfide rich stream can be introduced via line 462 to the sulfur recovery unit 466 for sulfur recovery. As an example, the sulfur recovery unit 466 can be an oxygen fired Claus unit. When the hydrogen sulfide stream in line 462 is combusted in the sulfur recovery unit 466 a tail gas can be produced. The tail gas can be compressed and recycled via line 468 upstream of the acid removal device 460.
A portion of the treated gas in line 118 can be removed via line 499 and used as a fuel gas. The fuel gas can be combusted to provide power for the SNG system 300. The remaining treated syngas in line 118 can be introduced to the methanator 500. The treated syngas can have a nitrogen content of 0 mol % to about 50 mol % and argon content ranging from about 0 mol % to a high of about 5 mol %.
A heat transfer medium via line 120 can be introduced to the methanator 500, as discussed and described above with reference to
In another embodiment, the methanation condensate in line 509 can be recycled back to the gas cooler 440, saturators 420, or other portions of the SNG system 300. The methanator 500 can provide high pressure steam via line 124 to the syngas cooler 305. The syngas cooler 305 can superheat the high pressure steam to provide superheated high pressure steam via line 110, as discussed and described above. The superheated high pressure steam can be introduced to one or more steam turbine generators to produce electricity for the SNG system 300.
In one or more embodiments, the methanator 500 can include one, two, three, four, five, six, or even twenty methanator reactors. The methanator 500 can also include various heat exchangers and mixing equipment to ensure that a proper temperature is maintained in each of the methanator reactors. The reactors can include a methanation catalyst. The methanation catalyst can include nickel, ruthenium, another common methanation catalyst material, or combinations thereof. The methanator 500 can be maintained at a temperature from about 150° C. to about 1,000° C. The methanator 500 can provide SNG via line 122 to the SNG drying and compression device 510.
In one or more embodiments, the methanator 500 can include three reactors arranged in parallel and a fourth reactor can be in series with three parallel reactors (not shown). The three parallel reactors can provide a portion of the total SNG introduced to the fourth reactor. The three reactors can also have a recycle stream, which can recycle a portion of the SNG back to the inlet of each of the three reactors. SNG can be provided from the fourth reactor via line 122 to the SNG drying and compression device 510.
The SNG drying and compression device 510 can dehydrate the SNG in line 122 to about 3.5 kilograms of water per million standard cubic meters (Mscm) or lower. The dehydration can be performed in a conventional tri-ethylene glycol unit. After dehydration the SNG in line 122 can be compressed, cooled, and introduced via line 512 to an end user or a pipeline. The SNG in line 512 can have a pressure ranging from about 1,379 kPa to about 12,411 kPa and a temperature of about 20° C. to about 75° C. In one or more embodiments, the SNG in line 122 can be compressed, and after compression the SNG in line 122 can be dehydrated.
Embodiments of the present invention can be further described with the following simulated processes. One or more of the above described systems can theoretically be used with Wyoming Powder River Basin (“WPRB”) coal. The WPRB coal was given a composition as shown in Table 1 below.
The simulated composition of the raw syngas via line 106 from the gasifier 205 was calculated to have a composition as shown in Table 2.
Based on simulated process conditions, when the syngas provided from the gasification of the WPRB coal, is processed in accordance to one or more embodiments discussed and described above, the treated syngas via line 118 introduced to the methanator 500 can have the composition shown in Table 3.
The calculated feed requirements and some of the by-product production for generating SNG, from WPRB coal, using a process according to one or more of the embodiments discussed and described above, can be as shown in Table 4. The feed requirements and by-product (carbon dioxide) generation were calculated using the assumption of a production of about 4.3 million standard cubic meters per day (Mscmd) of SNG with a heating value of about 36 MJ/scm.
AR is the calculated coal feed rate in tonnes per day as received, which had moisture content for WPRB coal of 27.21 wt %. AF is the calculated coal feed rate as the coal is introduced to the gasifier 205, which had moisture content for PRB coal of 17.89 wt %. The oxygen per tonne of coal was calculated on moisture and ash free basis. The calculated make-up water for the SNG system, which uses syngas derived from WPRB coal, is about 1.14 cubic meters per minute (CMPM). Fuel gas is treated syngas produced in excess of treated syngas need to meet the target SNG production of 4.3 Mscmd, which can be used as fuel for the SNG system. In addition to the by-product, carbon dioxide, listed in Table 4, other by-products produced using WPRB coal were calculated to include sulfur at a rate of about 33 tonne/day and ash at a rate of about 814 tonne/day.
One or more of the above described systems theoretically can be used with North Dakota Lignite Coal. The North Dakota Lignite Coal was given a composition as shown below in Table 5 below.
The simulated composition of the raw syngas via line 106 from the gasifier 205 was calculated to have a composition as shown in Table 6.
Based on simulated process conditions, when the raw syngas via line 106 from the gasification of the North Dakota Lignite is processed in accordance to one or more embodiments discussed and described above, the treated syngas via line 118 introduced the methanator 500 can have the composition shown in Table 7.
The calculated feed requirements and some of the by-products produced during the production of the SNG, from North Dakota Lignite Coal can be as shown in Table 8. The values in Table 8 were based on the use of three gasifiers 205. The feed requirements and by-product generation were calculated assuming a production of about 4.3 Mscmd of SNG with a heating value of about 36 MJ/scm.
AR is the calculated coal feed rate in tonnes per day as received, which had moisture content for the North Dakota lignite of 29.82 wt %. AF is the calculated coal feed rate as the coal is introduced to the gasifier 205, which had a moisture content for the North Dakota Lignite of 17.89 wt %. The oxygen per tonne of coal is calculated on a moisture and ash free basis. The calculated make-up water for the SNG system, which uses syngas derived from the North Dakota Lignite, is about 267 CMPM. In addition to the by-product (carbon dioxide) listed in Table 8, other by-products produced using North Dakota lignite were calculated to include sulfur at a rate of about 79 tonne/day and ash at a rate of about 1,521 tonne/day.
Simulated Auxiliary Power Requirements
The following section discusses the SNG facility's auxiliary power load requirements, power generation concepts, and options to meet the balance of power demand. The outside battery limit (“OSBL”) steam and power systems include the steam generation system and the electric power generation system. The inside battery limit (“ISBL”) process units produce substantial amounts of steam from waste heat recovery, which can be used to make electric power in one or more steam turbine generators (“STGs”). The specific configuration can depend on decisions regarding the electric power balance. For example, if sufficient electric power is reliably available at a competitive price from the local utility grid, the balance of the power demand can be purchased. However, if sufficient electric power is not reliably available, the SNG facility can be operated, electrically, in “island mode” and can generate all electrical power on-site. The island mode is possible with the SNG system, because the SNG system is more efficient than other SNG systems. The basic design options considered include:
Base Case—Purchase the balance of power requirements from the grid.
Option 1—Island operation with the balance of power provided via fired boilers and larger STGs.
Option 2—Island operation with the balance of power provided primarily via gas turbine generators (GTGs), heat recovery steam generators (HRSGs), and larger STGs.
Tables 9 and 10 summarize the basic performance parameters for the steam and power generation systems for the WPRB and North Dakota lignite cases.
WPRB Case Description
For the simulated WPRB coal case, there is a surplus of syngas (fuel gas) produced based on a target SNG production rate of 4.3 Mscmd. In the Base Case option, this surplus syngas is used as boiler fuel to produce more electric power via the STGs, and the balance of the electric power can be purchased off-site. In Options 1 & 2, the balance of power is generated on-site. With a fixed amount of syngas produced from the gasifiers, using syngas as fuel can reduce the net production of SNG in Option 1, as indicated. In Option 2, a small surplus of syngas is available after meeting the power generation requirements (i.e., Table 9 shows slightly more power generation than load for Option 2). This is due to the higher efficiency of Option 2 vs. Option 1. The excess syngas can be used to increase SNG production marginally or the cogen cycle can be de-tuned to keep the syngas requirement in balance. For example, the load on one or more GTGs can be reduced and duct firing for one or more HRSGs can be increased.
North Dakota Lignite Case Description
For the North Dakota lignite case, in the Base Case option, the balance of electric power is purchased from off-site. In Options 1 & 2 the balance of power is generated on-site. Since no additional fuel gas is available, the extra fuel requirement for Options 1 & 2 is shown as an equivalent reduction in SNG production.
Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account numerical error and variations that would be expected by a person having ordinary skill in the art.
Various terms have been defined above. To the extent, a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application is a continuation of co-pending U.S. patent application Ser. No. 12/437,999, filed on May, 8, 2009, which claims the benefit of U.S. Provisional Patent Application No. 61/081,304, filed on Jul. 16, 2008, which are both incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| 61081304 | Jul 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12437999 | May 2009 | US |
| Child | 13091980 | US |
