The present invention relates generally to processes for preparing an inorganic sodium and/or chlorine contaminated low-rank coal feedstock for combustion in a fluidized fuel combustor to generate steam and, desirably, co-generate electricity. Particularly, the present invention provides for optimal water usage and increased efficiency in such scenario by integrating low-pressure steam from the combustion (and optional electricity) generation section of the process with the feedstock processing section of the process, as well as integrating water recovery and recycle throughout the process.
Coal has long been used as a fuel for combustion. Currently, such coals are typically combusted with pressurized air and oxygen in fluidized fuel combustors such as circulating fluidized-bed combustors (“CFBs”) and pulverized coal boilers (“PCB”). CFBs generally operate at relatively moderate temperatures of from about 760° C. to about 930° C., and utilize “coarser” fuel particles having a dp(50) typically ranging from about 3000 microns to about 6000 microns. PCBs operate at higher temperatures of from about 1300° C. to about 1700° C., and utilize “finer” fuel particles having a dp(50) typically ranging from about 100 to about 200 microns.
The combustion results in heat energy that can be used to generate steam (e.g., a steam boiler) for a variety of uses, including for driving turbines to generate electricity. The combustion also produces hot gases that can be used to drive a turbine to generate electricity. A cogeneration facility is one in which both electricity and steam are made in order to more efficiently utilize the energy release of combustion, with the steam often being used to drive a steam turbine for additional electricity generation.
Many coals, however, are economically unfeasible for such use due to contamination and physical properties. For example, coals that contain significant amounts of impurities, such as sodium and chlorine (e.g., NaCl), may actually be unusable in combustion processes due to the highly corrosive and fouling nature of such components, thus requiring pretreatment to remove such impurities. Gaseous effluent streams from the combustion of such coals can also be problematic, particularly if the coal is not sufficiently cleaned prior to combustion. See, for example, Tillman, Duong, Figueroa and Miller, “Chlorine in Solid Fuels Fired in Pulverized Coal Boilers-Sources, Forms, Reactions, and Consequences: A Literature Review”, Foster Wheeler A G, Presented at Fuel Quality Conference, Banff, Canada, Sep. 28-Oct. 3, 2008.
While washing can be used in an attempt to clean such coals, the washing requires large amounts of fresh water which may not be economically feasible in many regions of the world, particularly those regions (arid areas, for example) where fresh water is at a premium. In addition, washing creates a number of wastewater issues.
Typically the addition of such a pretreatment renders the use of sodium and/or chlorine contaminated coals economically unfeasible. It would, therefore, be desirable to find a way to more efficiently pretreat these contaminated coals to removed a substantial portion of at least the inorganic sodium and/or chlorine content, while minimizing fresh water usage.
“Low-rank” coals are typically softer, friable materials with a dull, earthy appearance. They are characterized by relatively higher moisture levels and relatively lower carbon content, and therefore a lower energy content. Examples of low-rank coals include peat, lignite and sub-bituminous coals. Examples of “high-rank” coals include bituminous and anthracite coals.
In addition to their relatively low heating values, the use of low-ranks coals has other drawbacks. For example, the friability of such coals can lead to high fines losses in the feedstock preparation (grinding and other processing) and in the combustion of such coals. Such fines must be managed or even disposed of, which usually means an economic and efficiency disadvantage (economic and processing disincentive) to the use of such coals. For very highly friable coals such as lignite, such fines losses can approach or even exceed 50% of the original material. In other words, the processing and use of low-rank coals can result in a loss (or less desired use) of a material percentage of the carbon content in the low-rank coal as mined.
Low-rank coals contaminated with sodium and/or chlorine are, therefore, generally considered economically unsuitable for any purpose.
It would, therefore, be desirable to find a way to efficiently process sodium and/or chlorine contaminated low-rank coals to make such coals more economically feasible for combustion uses, while reducing or even eliminating fresh water requirements, as well as potentially reducing fines losses in both the feedstock processing and ultimate conversion of such low-rank coal materials in various combustion processes.
In a first aspect, the invention provides a process for generating steam from a particulate low-rank coal feedstock, the process comprising the steps of:
(a) providing a raw low-rank coal feedstock comprising an initial contaminant content, wherein the initial contaminant content comprises
(b) grinding the raw low-rank coal feedstock to produce a ground low-rank coal feedstock;
(c) washing the ground low-rank coal feedstock with an aqueous wash stream to generate a washed ground low-rank coal feedstock and a wastewater stream, the washed ground low-rank coal feedstock having
(d) contacting the washed ground low-rank coal feedstock with a dry gas stream and thermal energy in a thermal drying unit to generate a reduced-moisture washed ground low-rank coal feedstock and a moisture recovery stream, wherein at least a portion of the thermal energy is provided by a lower-pressure steam stream at a pressure of from about 10 psig (about 170 kPa absolute) to about 50 psig (about 446 kPa absolute), and wherein the reduced-moisture washed ground low-rank coal feedstock is free flowing with a moisture content no greater than about 40 wt % based on the total weight of the reduced-moisture washed ground low-rank coal feedstock;
(e) feeding the reduced-moisture washed ground low-rank coal feedstock and an oxygen-containing gas stream into a combustor;
(f) combusting the reduced-moisture low-rank coal feedstock in the combustor with oxygen to generate a combustion gas stream comprising steam, carbon dioxide and heat energy;
(g) recovering heat energy from the combustion gas stream by generating a higher-pressure steam stream at a pressure of at least about 150 psig (at least about 1136 kPa absolute),
(h) converting at least a portion of the higher-pressure steam stream to generate the lower-pressure steam stream;
(i) condensing at least a portion of the moisture recovery stream from step (d) to generate a condensed moisture stream;
(j) treating the wastewater stream from washing step (c) to generate a recovered water stream; and
(k) recycling (1) at least a portion of the condensed moisture stream, or (2) at least a portion of the recovered water stream, or (3) both (1) and (2), to the washing step (c), wherein the aqueous wash stream comprises at least in part the recycled portion of the condensed moisture stream and the recovered water stream.
The washing step (c) can occur (1) concurrently with and as a part of the grinding step (b), or (2) subsequent to the grinding step (b), or (3) both (1) and (2), but in any case before the “drying” step (d).
In one option, electricity is generated by flowing the combustion gas stream, either before or subsequent to heat recovery step (g), through a turbine that is connected to an electrical generator (with the mechanical energy generated by the turbine driving the generator).
In another option, electricity is generated by flowing the higher-pressure steam stream through a turbine that is connected to an electrical generator (with the mechanical energy generated by the turbine driving the generator).
In yet another option there is co-generation of electrical energy both from the combustion gas and the higher-pressure steam stream.
In yet another option, the raw low-rank coal feedstock has an initial moisture content, and the moisture content of the reduced-moisture washed ground low-rank coal feedstock is less than the initial moisture content of the raw low-rank coal feedstock (total wt/wt basis).
In yet another option, water can be recovered from the combustion gas by condensing at least a portion of the steam in the combustion gas. The condensation can occur, for example, as part of the heat recovery from the combustion gas, and/or subsequent thereto prior to discharge of the combustion gas from the process. Any recovered water can be sent to wastewater treatment and/or otherwise recycled back into the process.
As a consequence of steam generation and recycle for feedstock drying, and as a consequence of recycle of the moisture stream from the feedstock drying to the wash stage, the present invention provides the potential for increased efficiency and economic use of inorganic chlorine and/or inorganic sodium contaminated low-ranks coals in combustion processes where steam (and desirably electricity) are generated.
In addition, a portion of the moisture content from the raw low-rank coal feedstock can actually be recovered in the process of the present invention, particularly when the moisture content of the reduced-moisture washed ground low-rank coal feedstock is less than the initial moisture content of the raw low-rank coal feedstock. This reduces the fresh water demand of the overall process. In fact, depending on the difference between moisture contents of the raw low-rank coal feedstock and the reduced-moisture washed ground low-rank coal feedstock (and the optional recovery of moisture from the combustion gas), the present invention can provide a process that is water neutral or even water positive, which is highly desirable for operating coal combustion processes where fresh water is at a premium (for example, in arid environments).
These and other embodiments, features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed description.
The present invention relates to processes for preparing feedstocks from low-rank coals that are suitable for use in certain combustion processes, for combusting those prepared feedstocks to generate steam and optionally electricity, and for integrating the steam produced from the combustion section with the feedstock preparation section so as to minimize the amount of (or even eliminate) fresh water needed for the integrated process. Further details are provided below.
In the context of the present description, all publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.
Except where expressly noted, trademarks are shown in upper case.
Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
Unless stated otherwise, pressures expressed in psi units are gauge, and pressures expressed in kPa units are absolute. Pressure differences, however, are expressed as absolute (for example, pressure 1 is 25 psi higher than pressure 2).
When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range.
When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.
As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Further, unless expressly stated to the contrary, “or” and “and/or” refers to an inclusive and not to an exclusive. For example, a condition A or B, or A and/or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
The use of “a” or “an” to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
The term “substantial”, as used herein, unless otherwise defined herein, means that greater than about 90% of the referenced material, preferably greater than about 95% of the referenced material, and more preferably greater than about 97% of the referenced material. If not specified, the percent is on a molar basis when reference is made to a molecule (such as methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as for carbon content).
The term “predominant portion”, as used herein, unless otherwise defined herein, means that greater than 50% of the referenced material. If not specified, the percent is on a molar basis when reference is made to a molecule (such as hydrogen, methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as for carbon content).
The term “depleted” or “reduced” is synonymous with reduced from originally present. For example, removing a substantial portion of a material from a stream would produce a material-depleted stream that is substantially depleted of that material. Conversely, the term “enriched” or “increased” is synonymous with greater than originally present.
The term “carbonaceous” as used herein is synonymous with hydrocarbon.
The term “carbonaceous material” as used herein is a material containing organic hydrocarbon content. Carbonaceous materials can be classified as biomass or non-biomass materials as defined herein.
The term “biomass” as used herein refers to carbonaceous materials derived from recently (for example, within the past 100 years) living organisms, including plant-based biomass and animal-based biomass. For clarification, biomass does not include fossil-based carbonaceous materials, such as coal. For example, see US2009/0217575A1, US2009/0229182A1 and US2009/0217587A1.
The term “plant-based biomass” as used herein means materials derived from green plants, crops, algae, and trees, such as, but not limited to, sweet sorghum, bagasse, sugarcane, bamboo, hybrid poplar, hybrid willow, albizia trees, eucalyptus, alfalfa, clover, oil palm, switchgrass, sudangrass, millet, jatropha, and miscanthus (e.g., Miscanthus×giganteus). Biomass further include wastes from agricultural cultivation, processing, and/or degradation such as corn cobs and husks, corn stover, straw, nut shells, vegetable oils, canola oil, rapeseed oil, biodiesels, tree bark, wood chips, sawdust, and yard wastes.
The term “animal-based biomass” as used herein means wastes generated from animal cultivation and/or utilization. For example, biomass includes, but is not limited to, wastes from livestock cultivation and processing such as animal manure, guano, poultry litter, animal fats, and municipal solid wastes (e.g., sewage).
The term “non-biomass”, as used herein, means those carbonaceous materials which are not encompassed by the term “biomass” as defined herein. For example, non-biomass include, but is not limited to, anthracite, bituminous coal, sub-bituminous coal, lignite, petroleum coke, asphaltenes, liquid petroleum residues or mixtures thereof. For example, see US2009/0166588A1, US2009/0165379A1, US2009/0165380A1, US2009/0165361A1, US2009/0217590A1 and US2009/0217586A1.
“Liquid heavy hydrocarbon materials” are viscous liquid or semi-solid materials that are flowable at ambient conditions or can be made flowable at elevated temperature conditions. These materials are typically the residue from the processing of hydrocarbon materials such as crude oil. For example, the first step in the refining of crude oil is normally a distillation to separate the complex mixture of hydrocarbons into fractions of differing volatility. A typical first-step distillation requires heating at atmospheric pressure to vaporize as much of the hydrocarbon content as possible without exceeding an actual temperature of about 650° F. (about 343° C.), since higher temperatures may lead to thermal decomposition. The fraction which is not distilled at atmospheric pressure is commonly referred to as “atmospheric petroleum residue”. The fraction may be further distilled under vacuum, such that an actual temperature of up to about 650° F. (about 343° C.) can vaporize even more material. The remaining undistillable liquid is referred to as “vacuum petroleum residue”. Both atmospheric petroleum residue and vacuum petroleum residue are considered liquid heavy hydrocarbon materials for the purposes of the present invention.
Non-limiting examples of liquid heavy hydrocarbon materials include vacuum resids; atmospheric resids; heavy and reduced petroleum crude oils; pitch, asphalt and bitumen (naturally occurring as well as resulting from petroleum refining processes); tar sand oil; shale oil; bottoms from catalytic cracking processes; coal liquefaction bottoms; and other hydrocarbon feedstreams containing significant amounts of heavy or viscous materials such as petroleum wax fractions.
The term “asphaltene” as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, for example, from the processing of crude oil and crude oil tar sands. Asphaltenes may also be considered liquid heavy hydrocarbon feedstocks.
The liquid heavy hydrocarbon materials may inherently contain minor amounts of solid carbonaceous materials, such as petroleum coke and/or solid asphaltenes, that are generally dispersed within the liquid heavy hydrocarbon matrix, and that remain solid at the elevated temperature conditions utilized as the feed conditions for the present process.
The terms “petroleum coke” and “petcoke” as used herein include both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues—“resid petcoke”); and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands—“tar sands petcoke”). Such carbonization products include, for example, green, calcined, needle and fluidized bed petcoke.
Resid petcoke can also be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil (such as a liquid petroleum residue), which petcoke contains ash as a minor component, typically about 1.0 wt % or less, and more typically about 0.5 wt % of less, based on the weight of the coke. Typically, the ash in such lower-ash cokes predominantly comprises metals such as nickel and vanadium.
Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand. Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt % to about 12 wt %, and more typically in the range of about 4 wt % to about 12 wt %, based on the overall weight of the tar sands petcoke. Typically, the ash in such higher-ash cokes predominantly comprises materials such as silica and/or alumina.
Petroleum coke can comprise at least about 70 wt % carbon, at least about 80 wt % carbon, or at least about 90 wt % carbon, based on the total weight of the petroleum coke. Typically, the petroleum coke comprises less than about 20 wt % inorganic compounds, based on the weight of the petroleum coke.
The term “coal” as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof. In certain embodiments, the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight. In other embodiments, the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on the total coal weight. Examples of useful coal include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon, and Powder River Basin (PRB) coals. Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt %, from about 5 to about 7 wt %, from about 4 to about 8 wt %, and from about 9 to about 11 wt %, ash by total weight of the coal on a dry basis, respectively. However, the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, for example, “Coal Data: A Reference”, Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
The ash produced from combustion of a coal typically comprises both a fly ash and a bottom ash, as is familiar to those skilled in the art. The fly ash from a bituminous coal can comprise from about 20 to about 60 wt % silica and from about 5 to about 35 wt % alumina, based on the total weight of the fly ash. The fly ash from a sub-bituminous coal can comprise from about 40 to about 60 wt % silica and from about 20 to about 30 wt % alumina, based on the total weight of the fly ash. The fly ash from a lignite coal can comprise from about 15 to about 45 wt % silica and from about 20 to about 25 wt % alumina, based on the total weight of the fly ash. See, for example, Meyers, et al. “Fly Ash. A Highway Construction Material,” Federal Highway Administration, Report No. FHWA-IP-76-16, Washington, D.C., 1976.
The bottom ash from a bituminous coal can comprise from about 40 to about 60 wt % silica and from about 20 to about 30 wt % alumina, based on the total weight of the bottom ash. The bottom ash from a sub-bituminous coal can comprise from about 40 to about 50 wt % silica and from about 15 to about 25 wt % alumina, based on the total weight of the bottom ash. The bottom ash from a lignite coal can comprise from about 30 to about 80 wt % silica and from about 10 to about 20 wt % alumina, based on the total weight of the bottom ash. See, for example, Moulton, Lyle K. “Bottom Ash and Boiler Slag,” Proceedings of the Third International Ash Utilization Symposium, U.S. Bureau of Mines, Information Circular No. 8640, Washington, D.C., 1973.
A material such as methane can be biomass or non-biomass under the above definitions depending on its source of origin.
A “non-gaseous” material is substantially a liquid, semi-solid, solid or mixture at ambient conditions. For example, coal, petcoke, asphaltene and liquid petroleum residue are non-gaseous materials, while methane and natural gas are gaseous materials.
The term “unit” refers to a unit operation. When more than one “unit” is described as being present, those units are operated in a parallel fashion unless otherwise stated. A single “unit”, however, may comprise more than one of the units in series, or in parallel, depending on the context. For example, a cyclone unit may comprise an internal cyclone followed in series by an external cyclone. As another example, a pelletizing unit may comprise a first pelletizer to pelletize to a first particle size/particle density, followed in series by a second pelletizer to pelletize to a second particle size/particle density.
The term “free-flowing” particles as used herein means that the particles do not materially agglomerate (for example, do not materially aggregate, cake or clump) due to moisture content, as is well understood by those of ordinary skill in the relevant art. Free-flowing particles need not be “dry” but, desirably, the moisture content of the particles is substantially internally contained so that there is minimal (or no) surface moisture.
The term “superheated steam” in the context of the present invention refers to a steam stream that is non-condensing under the conditions utilized, as is commonly understood by persons of ordinary skill in the relevant art.
The term “dry saturated steam” or “dry steam” in the context of the present invention refers to slightly superheated saturated steam that is non-condensing, as is commonly understood by persons of ordinary skill in the relevant art.
The term “HGI” refers to the Hardgrove Grinding Index as measured in accordance with ASTM D409/D409M-11ae1.
The term “dp(50)” refers to the mean particle size of a particle size distribution as measured in accordance with ASTM D4749-87 (2007).
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein. The materials, methods, and examples herein are thus illustrative only and, except as specifically stated, are not intended to be limiting.
Low-Rank Coal Feedstock
The present invention in part is directed to various processes for processing raw low-rank coal feedstocks to form suitable processed low-rank coal feedstocks for combustion applications.
In step (a) the raw low-rank coal feedstock is provided.
The term “low-rank coal” is generally understood by those of ordinary skill in the relevant art. Low-rank coals include typical sub-bituminous coals, as well as lignites and peats. Low-ranks coals are generally considered to be “younger” coals than high-rank bituminous coal and anthracite, and tend to have lower particle density, higher porosity, lower fixed carbon content, higher moisture content, higher volatile content and, in many cases, higher inorganic ash content than such high rank coals.
In one embodiment, the raw low-rank coal feedstock has an inherent (total) moisture content of about 25 wt % or greater (as measured in accordance with ASTM D7582-10e1), a heating value of about 6500 kcal/kg (dry basis) or less (as measured in accordance with ASTM D5865-11a), and a fixed carbon content of about 45 wt % or less (as measured in accordance with ASTM D7582-10e1).
Typically, the raw low-rank particulate coal feedstocks will have an HGI of about 50 or greater. An embodiment of a low-rank coal for use in the present invention is a raw coal with an HGI of about 70 or greater, or from about 70 to about 130. In one embodiment, the low-rank coal is a lignite.
Typically, the raw particulate low-rank coal feedstock for use in the present processes will be substantially low-rank coal, or only low-rank coal. Mixtures of two or more different low-rank coals may also be used.
The raw low-rank coal feedstock (single or mixture) suitable for use in the present invention will possess an initial moisture content. The initial (inherent) moisture content of the raw low-rank coal feedstock is desirably high enough so that a portion of the inherent water content of the coal is recovered as a result of the drying step (d). In other words, the moisture content of the “processed” coal from the drying step should be less than the inherent moisture content of the raw low-rank coal going into the processing stage. In one embodiment, the initial moisture content of the raw low-rank coal feedstock is at least about 25 wt %, or at least about 30 wt %, or at least about 35 wt %, or at least about 40 wt %, based on total weight of the raw low-rank coal feedstock.
The raw low-rank coal feedstock (single or mixture) suitable for use in the present invention also possess and an initial contaminant content. The contaminant content of the raw low-rank coal feedstock has a chlorine component, or a sodium component, or both.
The chlorine component is an initial inorganic chlorine content of at least about 0.1 wt %, or at least about 0.2 wt %, or at least about 0.25 wt %, based on the dry weight of the raw low-rank coal feedstock. Desirably, the coal should also have an initial organic chlorine content of less than about 0.25 wt %, or less than about 0.2 wt %, or less than about 0.15 wt %, or less than about 0.1 wt %, based on the dry weight of the raw low-rank coal feedstock.
The sodium component is an initial inorganic sodium content of at least about 0.1 wt %, or at least about 0.2 wt %, or at least about 0.25 wt %, based on the dry weight of the raw low-rank coal feedstock.
Typically, when there is an inorganic chlorine component there is also a related inorganic sodium component, as inorganic chlorine is sometimes referred to as “salt chlorine”.
“Inorganic” with respect to sodium and chlorine content means generally not bound into the coal matrix via organic bonds such that the sodium and chlorine can be dissolved in water (and thus potentially removed by washing), as further detailed below.
Sodium content of a coal is determined in accordance with ASTM D4326-11. In the context of the present invention, “inorganic sodium content” is the sodium content of a coal sample measured in accordance with this ASTM method (all such measured sodium is considered to be inorganic for the purposes of the present invention).
Chlorine content of a coal is determined in accordance with ASTM D4208-13. In the context of the present invention, “total chlorine content” is the chlorine content measured in accordance with the ASTM standard on a raw (unwashed) coal sample. “Organic chlorine content” is the chlorine content measured in accordance with the ASTM standard on a water-washed coal sample (in other words, the amount of chlorine not readily removed via water washing). “Inorganic chlorine content” in the context of the present invention is the difference between “total chlorine content” and “organic chlorine content”.
For purposes of definition, the water washing of the coal sample for measuring the organic chlorine content is performed via the following procedure:
This process is repeated as necessary to collect sufficient sample sizes for analysis via ASTM D4208-13.
Mixtures of a predominant amount one or more low-rank coals with a minor amount of one or more other non-gaseous carbonaceous feedstocks may also be used. Such other non-gaseous feedstocks include, for example, high-rank coals, petroleum coke, liquid petroleum residues, asphaltenes and biomass. In the event of a combination of a low-rank coal with another type of non-gaseous carbonaceous material, the heating value from the low-rank coal component must be the predominant portion of the combination. Expressed another way, the overall heating value of a combination feedstock is greater than 50%, or greater than about 66%, or greater than about 75%, or greater than about 90%, from a low-rank coal source.
As discussed in more detail below, when utilized the certain other non-gaseous carbonaceous materials may be added at various other steps in the process. For example, when a pelletizing operation is present, such materials may be used to assist in the pelletizing (binding) of the ground low-rank coal feedstock, such as liquid petroleum residues, asphaltenes and certain biomasses such as chicken manure. Such materials can also be used to modify the other properties of the combination feedstock, such as overall carbon content, water content, ash content and other properties recognizable to those of ordinary skill in the relevant art.
The raw low-rank coal feedstock may be provided directly from a mine, or it may be pre-processed as is well-known in the art by a coarse grind more suitable for transport via rail, truck or conveyor.
General Feedstock Preparation Process Information
The raw low-rank coal feedstock provided in step (a) is initially processed by grinding to a desired initial particle size, washing, optionally pelletizing, drying then optionally sizing to the desired end particle size, an embodiment of which is depicted in
In accordance with that embodiment, a raw low-rank coal feedstock (10) as described above is provided and ground in step (b) to generate a ground low-rank coal feedstock of a specified particle size.
In the grinding step (b), the raw low-rank coal feedstock (10) can be crushed, ground and/or pulverized in a grinding unit (110) according to any methods known in the art, such as impact crushing and wet or dry grinding, to yield a ground low-rank coal feedstock (20) of a particle size distribution suitable for subsequent processing into a final particle size profile for the intended end use.
As indicated above, the raw low-rank coal feedstock (10) as provided to the grinding step may be as taken directly from a mine or may be initially processed, for example, by a coarse crushing to a particle size sufficiently large to be more finely ground in the grinding step.
A person of ordinary skill in the relevant end-use art will readily be able to determine the desired particle size profile for the desired end use. Different processes will have their own more narrow ranges of particle size distributions, as discussed in more detail below.
The ground low-rank coal feedstock (20) may optionally be sized directly after grinding to refine the particle size distribution by removing “coarse” and/or “fine” materials.
In one embodiment, the raw low-rank coal feedstock (10) is dry ground to a desired initial particle size profile.
In another embodiment, the raw low-rank coal feedstock (10) is wet ground by adding a stream (40) of an aqueous medium into the grinding process. Examples of suitable methods for wet grinding of coal feedstocks are well known to those of ordinary skilled in the relevant art.
In accordance with step (c) of the process, the ground low-rank coal feedstock is washed with an aqueous wash stream. This washing can take place as an integral part of a wet grinding process (washing step occurs concurrently with grinding step), in which case stream (40) is the aqueous wash stream. The wash stream containing removed contaminants is withdrawn as a wastewater stream (46).
Alternatively, such washing can take place after the grinding (and optional sizing) step in a washing unit (120), in which case stream (44) is the aqueous wash stream. The wash stream containing removed contaminants is withdrawn as a wastewater stream (42).
In addition, such washing can occur both as part of the grinding process as well as separately on the ground low-rank coal feedstock (before or after optional sizing).
As depicted in
Coal washing processes suitable for use in washing unit (120) are well known to those of ordinary skill in the relevant art. One suitable such process involves utilizing one or a series of vacuum belt filters, where the ground coal is transported on a vacuum belt while it is sprayed with an aqueous medium, typically recycle water recovered from the treatment of wastewater streams from the process (for example, from the treatment of wastewater stream (42) and/or wastewater stream (46)). Additives such as surfactants, flocculants and pelletizing aids can also be applied at this stage. For example, surfactants and flocculants can be applied to assist in dewatering in the vacuum belt filters and/or any subsequent dewatering stages.
The resulting washed ground low-rank coal feedstock (22) will typically be in the form of a wet filter cake or concentrated slurry with a high water content, that will typically require an initial dewatering stage (optional dewatering unit (130)) to remove a portion of the water content and generate an initial dewatered ground low-rank coal feedstock (34) having a water content suitable for subsequent processing.
Methods and equipment suitable for dewatering wet coal filter cakes and concentrated coal slurries in this dewatering stage are well-known to those of ordinary skill in the relevant art and include, for example, filtration (gravity or vacuum), centrifugation and fluid press methods and equipment. Hydrophobic organic compounds and solvents having an affinity for the coal particles can be used to promote dewatering.
A wastewater steam (38) generated from dewatering unit (130) can, for example, be sent to wastewater treatment unit (160) for treatment along with wastewater streams (42) and (46) to generate a cleaned water stream (54) and a concentrated contaminant stream (52).
Cleaned water stream (54) recovered from wastewater treatment unit (160) is desirably recycled for use elsewhere in the process. For example, all or a portion of cleaned water stream (54) is recycled as recycle water stream (56), which can be combined with fresh water stream (12) to generate a water feed stream (14) for use as aqueous wash stream (40) and/or (44). Alternatively or in addition, all or a portion of cleaned water stream (54) can be recycled to the combustion section of the process for use in generating steam, as discussed in more detail below.
Depending on the type and amount of contaminants in concentrated contaminant stream (52), that stream can desirably be further processed to recover some of the contaminant components, or disposed of in an acceptable manner.
Depending on the properties of the raw low-rank coal feedstock (for example, HGI) and the desired end use, it may be desirable to agglomerate washed ground low-rank coal feedstock (22) (or initial dewatered ground low-rank coal feedstock (34) if present) in a subsequent pelletization unit (135) to generate a pelletized low-rank coal feedstock (36) of a suitable particle size distribution for the ultimate end use. For the purposes of the present invention, agglomeration/pelletization refers to both pelletization and briquetting processes for agglomerating and increasing particle size, of types that are generally known to those of ordinary skill in the relevant art.
One particular process for preparing agglomerated low-rank coal feedstocks is disclosed in previously incorporated U.S. application Ser. No. 14/039,321, entitled A
When agglomerization is utilized, additional fines materials of appropriate particle size from other sources (not depicted) can be added into the process at various places prior to pelletization unit (135). For example, fines materials from other coal and/or petcoke processing operations can be combined with washed ground low-rank coal feedstock (22) (or initial dewatered ground low-rank coal feedstock (34) if present) to modify (e.g., further reduce) the water content and/or increase the carbon content of the same.
Binders of various sorts are typically utilized in the agglomeration step. Suitable binders are generally well-known to those of ordinary skill in the relevant art and include organic and inorganic binders. Organic binders include, for example, various starches, flocculants, natural and synthetic polymers, biomass such as chicken manure, and dispersed/emulsified oil materials such as a dispersed liquid petroleum resid. Inorganic binders include mineral binders.
The pelletizing step should result in wet agglomerated low-rank coal particles (36) having a dp(50) close to a target dp(50) for the desired end use, which dp(50) can be further refined by a sizing step as discussed below.
Depending on the moisture content of the wet agglomerated low-rank coal particles (23), those particles may or may not be free flowing, and/or may not be structurally stable, and/or may have too high a moisture content for the desired end use, and may optionally need to go through an additional intermediate dewatering stage in a dewatering unit (not depicted) to generate a dewatered agglomerated low-rank coal feedstock. Methods suitable for dewatering the wet agglomerated low-rank coal particles (32) in dewatering stage are well-known to those of ordinary skill in the relevant art and include, for example, filtration (gravity or vacuum), centrifugation and fluid press.
In accordance with step (d) of the process, the washed ground low-rank coal feedstock (22) (or initial dewatered ground low-rank coal feedstock (34) if dewatering unit (130) is present, or wet agglomerated low-rank coal particles (36) if pelletizing unit (135) is present) is dried in a thermal drying unit (140) by contact with a gas stream (80) and that utilizes a lower-pressure steam stream (48) as a heat source, to generated a reduced-moisture washed ground low-rank coal feedstock (78), a recovery steam stream (50) and a recovered moisture stream (82). Sufficient moisture is removed so that the resulting reduced-moisture washed ground low-rank coal feedstock (78) is a free-flowing particulate. The amount of moisture necessary for removal can be readily determined by a person of ordinary skill in the art based on the composition and properties of the material entering thermal drying unit (140).
In accordance with the present invention, lower-pressure steam stream (48) is a steam stream derived and recycled from the combustion section of the present process, as discussed in more detail below.
The thermal drying unit (140) is typically a fluidized-bed dryer in which the coal particles are fluidized by gas stream (80) fed into thermal drying unit (140). Gas stream (80) is typically a “dry” air or nitrogen-enriched gas stream, for example, nitrogen-enriched stream (570) from an air separation unit (550) as shown in
Gas stream (80) is typically provided at slightly elevated pressures, for example, at pressures slightly above atmospheric up to about 50 psig (about 446 kPa absolute), or up to about 30 psig (about 308 kPa absolute), or up to about 15 psig (about 205 kPa absolute).
The lower-pressure steam stream (48) is provided at a pressure of from about 10 psig (about 170 kPa absolute), or about 15 psig (about 205 kPa absolute), to about 50 psig (about 446 kPa absolute), or to about 40 psig (about 377 kPa absolute), or to about 30 psig (about 308 kPa absolute).
The combination of the dry gas in gas stream (80) plus the heat energy transferred from lower-pressure steam stream (48) is sufficient to remove the desired amount of moisture from the wet feed to generate a reduced-moisture washed ground low-rank coal feedstock (78) that is free flowing. Desirably, the amounts of lower-pressure steam stream (48) and gas stream fed into thermal drying unit (140) are sufficient in combination so that the resulting reduced-moisture washed ground low-rank coal feedstock (78) has a moisture content of less than the initial moisture content of the raw low-rank coal feedstock (10), but no greater than about 40 wt %, or no greater than about 35 wt %, or nor greater than about 30 wt %, based on the total weight of the reduced-moisture washed ground low-rank coal feedstock (78).
Recovery steam stream (50) from thermal drying unit (140) is desirably recycled back into the process, either as a recycle steam stream (74) back to the combustion section of the process, and/or as recycle steam stream (58) back to the feedstock preparation stage, for example, as part of aqueous stream (40) and/or (44). When recycled back for use in the feedstock preparation stage, recycle seam stream (58) is very low-grade steam which is typically condensed to water, for example, via an air-cooled condensor (170) to generate a recycle water stream (76). Recovery steam stream (50) may also or alternatively be recycled in whole or part to water treatment unit (160) after being condensed.
The moisture in recovered moisture stream (82) is also desirably recycled back into the process. Typically, this moisture is condensed to water, for example, via an air-cooled condensor (180) to generate a recycle water stream (84) that is typically fed into water treatment unit (160) after being condensed. Recycle water stream may also or alternatively be recycled in whole or part back to the feedstock preparation stage, for example, as part of aqueous stream (40) and/or (44). The gas from which the moisture has been condensed can then be recycled as gas stream (80), optionally in combination with makeup gas from stream (570).
Typically, but optionally, a final sizing stage in a sizing unit (150) is provided to refine the particle distribution of the reduced-moisture washed ground low-rank coal feedstock (78), where all or a portion of particles above a target upper end size (large or “bigs”) (stream (70)) and below a target lower end particle size (fines or “smalls”) (stream (72)) are removed to result in the low-rank coal feedstock (32) for feeding into a combustor. Methods suitable for sizing are generally known to those of ordinary skill in the relevant art, and typically include screening units with appropriately sized screens. In one embodiment, at least 90 wt %, or at least 95 wt %, of either or both (desirably) of the bigs and smalls (based on a defined particle size distribution for low-rank coal feedstock (32) as fed into the combustion section of the process) are removed in this final sizing stage.
Other than any thermal drying, which takes place at elevated temperature and pressure conditions, all operations in the feedstock preparation stage generally take place under ambient temperature and pressure conditions. In one embodiment, however, the washing stage can take place under elevated temperature conditions (for example, using heated wash water) to promote dissolution of contaminants being remove during the washing process.
As indicated above, the final particle size distribution, well as other properties such as moisture content, for low-rank coal feedstock (32) will be specified for the ultimate end use, and will depend on factors such as the type of combustor, feedstock physical and chemical properties, and other known factors as will be recognized and understood by a person of ordinary skill in the relevant art.
In one embodiment, the resulting low-rank coal feedstock (32) has a particle size distribution suitable for a circulating fluidized-bed combustor, for example, a dp(50) which is a value in the range of from about 3000 microns to about 6000 microns.
In another embodiment, the resulting low-rank coal feedstock (32) has a particle size distribution suitable for a pulverized coal boiler, for example, a dp(50) which is a value in the range of from about 100 microns to about 200 microns.
Desirably, the combination of recycle water stream (56) and recycle steam stream (58) (or recycle water stream (76) if recycle steam stream (58) has been condensed) is such as to minimize or even eliminate fresh water stream (12). In one embodiment, the overall process is substantially water neutral in that substantially no fresh water is added in steady state operation of the process, for example, where fresh water stream (12) is about 5 wt % or less, or about 2 wt % or less, or about 0 wt %, based on the combined weight of fresh water stream (12), recycle water stream (56) and recycle steam stream (58) (or recycle water stream (76) if recycle steam stream (58) has been condensed). In another embodiment, the overall process is water positive in that water can actually be removed from the system, for example, as a portion of cleaned water stream (54), and used elsewhere.
Combustion Processes
As a general concept, in combustion processes the carbon in coal is burned for heat which can be recovered, for example, to generate steam various industrial uses, including but not limited to electricity generation, and for exhaust gases that can be used to drive turbines for electricity generation.
Suitable combustion technologies, operating conditions, and equipment and configurations, are generally known to those of ordinary skill in the relevant art, and many applicable technologies are commercially available.
On such technology utilizes a circulating fluidized-bed combustor (“CFB”). CFBs generally operate at relatively moderate temperatures typically ranging from about 760° C. to about 930° C. CFBs typically utilize coarser particles having a dp(50) ranging from about 3000 microns to about 6000 microns.
Another technology utilizes a pulverized coal boiler (“PCB”). PCBs operate at high temperatures typically ranging from about 1300° C. to about 1700° C. PCBs typically utilize finer particles having a dp(50) ranging from about 100 to about 200 microns.
The combustors can be operated at various pressures ranging from atmospheric to much higher pressure conditions, and typically use air for the fluidizing medium, which is typically enriched in oxygen to promote combustion.
All combustion processes will involve a reactor (combustor), which is generically depicted as (500) in
Referring to
In
Depending on the particular process, the low-rank coal feedstock (32) may be fed into combustion reactor (500) at one or more different locations optimized for the particular combustion process, as will be recognized by a person of ordinary skill in the relevant art.
The combustion in combustion reactor (500) will typically occur in a bed (502) of the feedstock (32) that is fluidized by the flow of the air or oxygen-enriched air stream (552) and/or other fluidizing gases (like carbon dioxide and/or nitrogen) that may be fed to combustion reactor (500).
Typically, combustion is a non-catalytic process, so no catalyst needs to be added to the feedstock (32) or into combustion reactor (500); however, a catalyst that promotes combustion may be utilized.
Typically, carbon conversion is substantially complete in combustion processes, and any residual solid residues are predominantly inorganic ash with little or no carbon residue. Depending on reaction conditions, combustion may be slagging or non-slagging, where a residue (514) is withdrawn from combustion reactor (500) as a molten (slagging) or solid (non-slagging) ash or char (to the extent there is still appreciable carbon content in the solid residue). Typically the residue is collected in a section (506) below bed (502) and withdrawn from the bottom of combustion reactor (500), but ash may also be withdrawn from the top (504) of combustion reactor (500) along with the raw combustion gas stream (510).
Section (506) and fluidized bed (502) can be separated, for example, by a grid plate (508).
The raw combustion gas stream (510) is typically withdrawn from the top or upper portion (504) of combustion reactor (500).
The hot gas effluent leaving bed (502) of combustion reactor (500) can pass through a fines remover unit (such as cyclone assembly (530)), incorporated into and/or external of combustion reactor (500), which serves as a disengagement zone. Particles too heavy to be entrained by the gas leaving combustion reactor (500) can be returned to combustion reactor (500), for example, to bed (502).
Residual entrained fines are substantially removed by any suitable device such as internal and/or external cyclone separators (530) to generate a fines-depleted raw combustion gas stream (516). At least a portion of these fines can be returned to bed (502) via recycle lines (562) and (566), particularly to the extent that such fines still contain material carbon content (can be considered char). Alternatively, any fines or ash (572) can be removed via line (562).
As set forth in
Turbine (542) may also desirably be mechanically connected to an air compressor (548) or similar device by a shaft (556) or other mechanical coupling, and the mechanical energy generated by turbine (542) drives air compressor (548) to compress an air stream (546) and generate a compressed air stream (568) for feeding back into combustion reactor (500) as air stream (552). Compressed air stream (568) can optionally be fed into an air separation device (550), for example a membrane or cryogenic separator, to enrich the oxygen content of compressed air stream (568) for use as oxygen-enriched stream (552). In one embodiment, air separation device (550) is a cryogenic separator, and electricity generated from the process can be used to power that unit.
The separated out gaseous components, shown as stream (570) and which will be predominantly nitrogen, can be discharged or used elsewhere in the process, for example, as stream (80) or makeup gas for stream (80) for use in thermal drying unit (140) as discussed above.
The exhaust gas (578) exiting turbine (542) still contains substantial heat energy, which can be recovered, for example, in a heat recovery steam generator (“HSRG”) (560). HSRGs are in a general sense well known to those of ordinary skill in the relevant art. For example, exhaust gas (578) can fed through heating coils (not depicted) in HSRG (560) to generate steam or further heat steam from an aqueous stream (62), which can be water and/or steam, fed into HSRG (560) to generate steam stream (524) and a reduced heat exhaust gas stream (522). As reduced heat exhaust gas stream (522) will typically contains a significant amount of water content (as steam), stream (522) can be passed through a cooling unit (574), such as an air cooling unit of a type well known to those of ordinary skill in the relevant art, to condense out moisture and generate a water recovery stream (582) and a cooled exhaust gas stream (580).
Cooled exhaust gas stream (580) is typically discharged to the atmosphere, but can be further treated by known processes prior to discharge.
Water recovery stream (582) is also desirably recycled back into the process. Typically, water recovery stream (582) will be fed into water treatment unit (160), as shown in
Steam stream (524) is typically a medium pressure steam stream that can be fed into a second turbine (540) which is connected to an electrical generator (558) by a shaft (580) or other mechanical coupling, and the mechanical energy generated by turbine (540) drives generator (558) so that electrical power (560) is produced.
Lower pressure steam stream (48) exits turbine (540) which, as shown in
A portion of lower pressure steam stream (48) can also be recycled back to HSRG (560) as stream (60), which can be combined with a portion of cleaned water stream (54) and/or recycle steam stream (74) for use as aqueous stream (62). Desirably, however, a portion of cleaned water stream (54) and/or recycle steam stream (74) can also be used as aqueous stream (62) without utilizing any of lower pressure steam stream (48) so that the thermal energy use of lower pressure steam stream (48) can be maximized in thermal drying unit (140).
Referring now to
In
Depending on the particular process, the low-rank coal feedstock (32) may be fed into combustion reactor (400) at one or more different locations optimized for the particular combustion process, as will be recognized by a person of ordinary skill in the relevant art.
The combustion in combustion reactor (400) will typically occur in a bed (402) of the feedstock (32) that is fluidized by the flow of the air or oxygen-enriched air stream (406) and/or other fluidizing gases (like carbon dioxide and/or nitrogen) that may be fed to combustion reactor (400).
Typically, combustion is a non-catalytic process, so no catalyst needs to be added to the feedstock (32) or into combustion reactor (400); however, a catalyst that promotes combustion may be utilized.
Typically, carbon conversion is substantially complete in combustion processes, and any residual solid residues are predominantly inorganic ash with little or no carbon residue. Depending on reaction conditions, combustion may be slagging or non-slagging, where a solid residue (414) is withdrawn from combustion reactor (400) as a molten (slagging) or solid (non-slagging) ash or char (to the extent there is still appreciable carbon content in the solid residue). Typically the residue is collected in a section (416) below bed (402) and withdrawn from the bottom of combustion reactor (400), but ash may also be withdrawn from the top (404) of combustion reactor (400) along with the raw combustion gas stream (410).
Section (406) and fluidized bed (402) can be separated, for example, by a grid plate (408).
The raw combustion gas stream (410) is typically withdrawn from the top or upper portion (404) of combustion reactor (400).
The hot gas effluent leaving bed (402) of combustion reactor (400) can pass through a fines remover unit (such as cyclone assembly (460)), incorporated into and/or external of combustion reactor (400), which serves as a disengagement zone. Particles too heavy to be entrained by the gas leaving combustion reactor (400) can be returned to combustion reactor (400), for example, to bed (402).
Residual entrained fines are substantially removed by any suitable device such as internal and/or external cyclone separators (460) to generate a fines-depleted raw combustion gas stream (430). At least a portion of these fines can be returned to bed (402) via recycle lines (462) and (466), particularly to the extent that such fines still contain material carbon content (can be considered char). Alternatively, any fines or ash (472) can be removed via line (462).
As set forth in
In the configuration of
A lower pressure steam stream (432) exits turbine (434), which is used in whole or part as lower-pressure steam stream (48) for feeding into thermal drying unit (140) as discussed above.
That portion of high-pressure steam stream (424) not fed into turbine (434) can be removed as steam stream (472) and utilized elsewhere. Generally, in the configuration of
A portion of lower pressure steam stream (432) can also be recycled back to heat exchanger (412) as stream (422), which can be combined with a portion of cleaned water stream (54) and/or recycle steam stream (74) for use as stream (422). Desirably, however, a portion of cleaned water stream (54) and/or recycle steam stream (74) can also be used as stream (422) without utilizing any of lower pressure steam stream (432) so that all of stream (432) is used as lower pressure steam stream (48), and the thermal energy use of lower pressure steam stream (48) can be maximized in thermal drying unit (140).
Fines-depleted raw combustion gas stream (430) still contains substantial heat energy as well as steam, and can be further processed to mechanically drive a turbine for electrical power generation and/or to drive an air compressor, and/or recover heat energy and/or steam in a similar fashion as set forth above in connection with the discussion of
Multi-Train Processes
In the processes of the invention, each process may be performed in one or more processing units. For example, one or more combustors may be supplied with the feedstock from one or more feedstock preparation unit operations.
In certain embodiments, the processes utilize two or more combustors (e.g., 2-4 combustors). In such embodiments, the processes may contain divergent processing units (i.e., less than the total number of combustors) prior to the combustors for ultimately providing the feedstock to the plurality of combustors, and/or convergent processing units (i.e., less than the total number of combustors) following the combustors for processing the plurality of combustion gas streams generated by the plurality of combustors.
When the systems contain convergent processing units, each of the convergent processing units can be selected to have a capacity to accept greater than a 1/n portion of the total feed stream to the convergent processing units, where n is the number of convergent processing units. Similarly, when the systems contain divergent processing units, each of the divergent processing units can be selected to have a capacity to accept greater than a 1/m portion of the total feed stream supplying the convergent processing units, where m is the number of divergent processing units.
This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Ser. Nos. 61/708,104 (filed 1 Oct. 2012), 61/775,771 (filed 11 Mar. 2013) and 61/815,800 (filed 25 Apr. 2013), the disclosures of which are incorporated by reference herein for all purposes as if fully set forth. This application is related to U.S. application Ser. No. 14/039,321, entitled AGGLOMERATED PARTICULATE LOW-RANK COAL FEEDSTOCK AND USES THEREOF), now U.S. Pat. No. 9,034,061; U.S. application Ser. No. 14/039,402, entitled AGGLOMERATED PARTICULATE LOW-RANK COAL FEEDSTOCK AND USES THEREOF); and U.S. application Ser. No. 14/039,454, entitled AGGLOMERATED PARTICULATE LOW-RANK COAL FEEDSTOCK AND USES THEREOF), now U.S. Pat. No. 9,034,058, all of which are concurrently filed herewith and incorporated by reference herein for all purposes as if fully set forth.
Number | Name | Date | Kind |
---|---|---|---|
2605215 | Coghlan | Jul 1952 | A |
2694623 | Welty, Jr. et al. | Nov 1954 | A |
2791549 | Jahnig | May 1957 | A |
2813126 | Tierney | Nov 1957 | A |
2860959 | Pettyjohn et al. | Nov 1958 | A |
2886405 | Benson et al. | May 1959 | A |
3034848 | King | May 1962 | A |
3114930 | Oldham et al. | Dec 1963 | A |
3150716 | Strelzoff et al. | Sep 1964 | A |
3164330 | Neidl | Jan 1965 | A |
3351563 | Negra et al. | Nov 1967 | A |
3435590 | Smith | Apr 1969 | A |
3531917 | Grunewald et al. | Oct 1970 | A |
3544291 | Schlinger et al. | Dec 1970 | A |
3594985 | Ameen et al. | Jul 1971 | A |
3615300 | Holm et al. | Oct 1971 | A |
3689240 | Aldridge et al. | Sep 1972 | A |
3740193 | Aldridge et al. | Jun 1973 | A |
3746522 | Donath | Jul 1973 | A |
3759036 | White | Sep 1973 | A |
3779725 | Hegarty et al. | Dec 1973 | A |
3814725 | Zimmerman et al. | Jun 1974 | A |
3817725 | Sieg et al. | Jun 1974 | A |
3828474 | Quartulli | Aug 1974 | A |
3833327 | Pitzer et al. | Sep 1974 | A |
3847567 | Kalina et al. | Nov 1974 | A |
3876393 | Kasai et al. | Apr 1975 | A |
3904386 | Graboski et al. | Sep 1975 | A |
3915670 | Lacey et al. | Oct 1975 | A |
3920229 | Piggott | Nov 1975 | A |
3929431 | Koh et al. | Dec 1975 | A |
3958957 | Koh et al. | May 1976 | A |
3966875 | Bratzler et al. | Jun 1976 | A |
3969089 | Moss et al. | Jul 1976 | A |
3971639 | Matthews | Jul 1976 | A |
3972693 | Wiesner et al. | Aug 1976 | A |
3975168 | Gorbaty | Aug 1976 | A |
3985519 | Kalina et al. | Oct 1976 | A |
3989811 | Hill | Nov 1976 | A |
3996014 | Muller et al. | Dec 1976 | A |
3998607 | Wesselhoft et al. | Dec 1976 | A |
3999607 | Pennington et al. | Dec 1976 | A |
4005996 | Hausberger et al. | Feb 1977 | A |
4011066 | Bratzler et al. | Mar 1977 | A |
4017272 | Anwer et al. | Apr 1977 | A |
4021370 | Harris et al. | May 1977 | A |
4025423 | Stonner et al. | May 1977 | A |
4044098 | Miller et al. | Aug 1977 | A |
4046523 | Kalina et al. | Sep 1977 | A |
4052176 | Child et al. | Oct 1977 | A |
4053554 | Reed et al. | Oct 1977 | A |
4057512 | Vadovic et al. | Nov 1977 | A |
4069304 | Starkovish et al. | Jan 1978 | A |
4077778 | Nahas et al. | Mar 1978 | A |
4091073 | Winkler | May 1978 | A |
4092125 | Stambaugh et al. | May 1978 | A |
4094650 | Koh et al. | Jun 1978 | A |
4100256 | Bozzelli et al. | Jul 1978 | A |
4101449 | Noda et al. | Jul 1978 | A |
4104201 | Banks et al. | Aug 1978 | A |
4113615 | Gorbaty | Sep 1978 | A |
4116996 | Huang | Sep 1978 | A |
4118204 | Eakman et al. | Oct 1978 | A |
4152119 | Schulz | May 1979 | A |
4157246 | Eakman et al. | Jun 1979 | A |
4159195 | Clavenna | Jun 1979 | A |
4162902 | Wiesner et al. | Jul 1979 | A |
4173465 | Meissner et al. | Nov 1979 | A |
4189307 | Marion | Feb 1980 | A |
4192652 | Smith | Mar 1980 | A |
4193771 | Sharp et al. | Mar 1980 | A |
4193772 | Sharp | Mar 1980 | A |
4200439 | Lang | Apr 1980 | A |
4204843 | Neavel | May 1980 | A |
4211538 | Eakman et al. | Jul 1980 | A |
4211669 | Eakman et al. | Jul 1980 | A |
4219338 | Wolfs et al. | Aug 1980 | A |
4223728 | Pegg | Sep 1980 | A |
4225457 | Schulz | Sep 1980 | A |
4235044 | Cheung | Nov 1980 | A |
4243639 | Haas et al. | Jan 1981 | A |
4249471 | Gunnerman | Feb 1981 | A |
4252771 | Lagana et al. | Feb 1981 | A |
4260421 | Brown et al. | Apr 1981 | A |
4265868 | Kamody | May 1981 | A |
4270937 | Adler et al. | Jun 1981 | A |
4284416 | Nahas | Aug 1981 | A |
4292048 | Wesselhoft et al. | Sep 1981 | A |
4298584 | Makrides | Nov 1981 | A |
4315753 | Bruckenstein et al. | Feb 1982 | A |
4315758 | Patel et al. | Feb 1982 | A |
4318712 | Lang et al. | Mar 1982 | A |
4322222 | Sass | Mar 1982 | A |
4330305 | Kuessner et al. | May 1982 | A |
4331451 | Isogaya et al. | May 1982 | A |
4334893 | Lang | Jun 1982 | A |
4336034 | Lang et al. | Jun 1982 | A |
4336233 | Appl et al. | Jun 1982 | A |
4341531 | Duranleau et al. | Jul 1982 | A |
4344486 | Parrish | Aug 1982 | A |
4347063 | Sherwood et al. | Aug 1982 | A |
4348486 | Calvin et al. | Sep 1982 | A |
4348487 | Calvin et al. | Sep 1982 | A |
4353713 | Cheng | Oct 1982 | A |
4365975 | Williams et al. | Dec 1982 | A |
4372755 | Tolman et al. | Feb 1983 | A |
4375362 | Moss | Mar 1983 | A |
4385905 | Tucker | May 1983 | A |
4397656 | Ketkar | Aug 1983 | A |
4400182 | Davies et al. | Aug 1983 | A |
4407206 | Bartok et al. | Oct 1983 | A |
4412840 | Goksel | Nov 1983 | A |
4428535 | Venetucci | Jan 1984 | A |
4432773 | Euker, Jr. et al. | Feb 1984 | A |
4433065 | Van der Burgt et al. | Feb 1984 | A |
4436028 | Wilder | Mar 1984 | A |
4436531 | Estabrook et al. | Mar 1984 | A |
4439210 | Lancet | Mar 1984 | A |
4443415 | Queneau et al. | Apr 1984 | A |
4444568 | Beisswenger et al. | Apr 1984 | A |
4459138 | Soung | Jul 1984 | A |
4462814 | Holmes et al. | Jul 1984 | A |
4466828 | Tamai et al. | Aug 1984 | A |
4468231 | Bartok et al. | Aug 1984 | A |
4478425 | Benko | Oct 1984 | A |
4478725 | Velling et al. | Oct 1984 | A |
4482529 | Chen et al. | Nov 1984 | A |
4491609 | Degel et al. | Jan 1985 | A |
4497784 | Diaz | Feb 1985 | A |
4500323 | Siegfried et al. | Feb 1985 | A |
4505881 | Diaz | Mar 1985 | A |
4508544 | Moss | Apr 1985 | A |
4508693 | Diaz | Apr 1985 | A |
4514912 | Janusch | May 1985 | A |
4515604 | Eisenlohr et al. | May 1985 | A |
4515764 | Diaz | May 1985 | A |
4524050 | Chen et al. | Jun 1985 | A |
4540681 | Kustes et al. | Sep 1985 | A |
4541841 | Reinhardt | Sep 1985 | A |
4551155 | Wood et al. | Nov 1985 | A |
4558027 | McKee et al. | Dec 1985 | A |
4572826 | Moore | Feb 1986 | A |
4594140 | Cheng | Jun 1986 | A |
4597775 | Billimoria et al. | Jul 1986 | A |
4597776 | Ullman et al. | Jul 1986 | A |
4604105 | Aquino et al. | Aug 1986 | A |
4609388 | Adler et al. | Sep 1986 | A |
4609456 | Deschamps et al. | Sep 1986 | A |
4617027 | Lang | Oct 1986 | A |
4619864 | Hendrix et al. | Oct 1986 | A |
4620421 | Brown et al. | Nov 1986 | A |
4661237 | Kimura et al. | Apr 1987 | A |
4668428 | Najjar | May 1987 | A |
4668429 | Najjar | May 1987 | A |
4675035 | Apffel | Jun 1987 | A |
4678480 | Heinrich et al. | Jul 1987 | A |
4682986 | Lee et al. | Jul 1987 | A |
4690814 | Velenyi et al. | Sep 1987 | A |
4696678 | Koyama et al. | Sep 1987 | A |
4699632 | Babu et al. | Oct 1987 | A |
4704136 | Weston et al. | Nov 1987 | A |
4720289 | Vaugh et al. | Jan 1988 | A |
4747938 | Khan | May 1988 | A |
H000478 | Blytas | Jun 1988 | H |
4781731 | Schlinger | Nov 1988 | A |
4803061 | Najjar et al. | Feb 1989 | A |
4808194 | Najjar et al. | Feb 1989 | A |
4810475 | Chu et al. | Mar 1989 | A |
4822935 | Scott | Apr 1989 | A |
4848983 | Tomita et al. | Jul 1989 | A |
4854944 | Strong | Aug 1989 | A |
4861346 | Najjar et al. | Aug 1989 | A |
4861360 | Apffel | Aug 1989 | A |
4872886 | Henley et al. | Oct 1989 | A |
4876080 | Paulson | Oct 1989 | A |
4892567 | Yan | Jan 1990 | A |
4960450 | Schwarz et al. | Oct 1990 | A |
4995193 | Soga et al. | Feb 1991 | A |
5017282 | Delbianco et al. | May 1991 | A |
5055181 | Maa et al. | Oct 1991 | A |
5057294 | Sheth et al. | Oct 1991 | A |
5059406 | Sheth et al. | Oct 1991 | A |
5074357 | Haines | Dec 1991 | A |
5093094 | Van Kleeck et al. | Mar 1992 | A |
5094737 | Bearden, Jr. et al. | Mar 1992 | A |
5132007 | Meyer et al. | Jul 1992 | A |
5223173 | Jeffrey | Jun 1993 | A |
5225044 | Breu | Jul 1993 | A |
5236557 | Muller et al. | Aug 1993 | A |
5242470 | Salter et al. | Sep 1993 | A |
5250083 | Wolfenbarger et al. | Oct 1993 | A |
5277884 | Shinnar et al. | Jan 1994 | A |
5354345 | Nehls, Jr. | Oct 1994 | A |
5388645 | Puri et al. | Feb 1995 | A |
5388650 | Michael | Feb 1995 | A |
5435940 | Doering et al. | Jul 1995 | A |
5505746 | Chriswell | Apr 1996 | A |
5536893 | Gudmundsson | Jul 1996 | A |
5566755 | Seidle et al. | Oct 1996 | A |
5616154 | Elliott et al. | Apr 1997 | A |
5630854 | Sealock, Jr. et al. | May 1997 | A |
5641327 | Leas | Jun 1997 | A |
5660807 | Forg et al. | Aug 1997 | A |
5669960 | Couche | Sep 1997 | A |
5670122 | Zamansky et al. | Sep 1997 | A |
5720785 | Baker | Feb 1998 | A |
5733515 | Doughty et al. | Mar 1998 | A |
5769165 | Bross et al. | Jun 1998 | A |
5776212 | Leas | Jul 1998 | A |
5788724 | Carugati et al. | Aug 1998 | A |
5855631 | Leas | Jan 1999 | A |
5865898 | Holtzapple et al. | Feb 1999 | A |
5968465 | Koveal et al. | Oct 1999 | A |
6013158 | Wootten | Jan 2000 | A |
6015104 | Rich, Jr. | Jan 2000 | A |
6028234 | Heinemann et al. | Feb 2000 | A |
6032737 | Brady et al. | Mar 2000 | A |
6090356 | Jahnke et al. | Jul 2000 | A |
6119778 | Seidle et al. | Sep 2000 | A |
6132478 | Tsurui et al. | Oct 2000 | A |
6180843 | Heinemann et al. | Jan 2001 | B1 |
6187465 | Galloway | Feb 2001 | B1 |
6379645 | Bucci et al. | Apr 2002 | B1 |
6389820 | Rogers et al. | May 2002 | B1 |
6419888 | Wyckoff | Jul 2002 | B1 |
6506349 | Khanmamedov | Jan 2003 | B1 |
6506361 | Machado et al. | Jan 2003 | B1 |
6602326 | Lee et al. | Aug 2003 | B2 |
6641625 | Clawson et al. | Nov 2003 | B1 |
6653516 | Yoshikawa et al. | Nov 2003 | B1 |
6692711 | Alexion et al. | Feb 2004 | B1 |
6790430 | Lackner et al. | Sep 2004 | B1 |
6797253 | Lyon | Sep 2004 | B2 |
6808543 | Paisley | Oct 2004 | B2 |
6830597 | Green | Dec 2004 | B1 |
6855852 | Jackson et al. | Feb 2005 | B1 |
6878358 | Vosteen et al. | Apr 2005 | B2 |
6894183 | Choudhary et al. | May 2005 | B2 |
6955595 | Kim | Oct 2005 | B2 |
6955695 | Nahas | Oct 2005 | B2 |
6969494 | Herbst | Nov 2005 | B2 |
7056359 | Somerville et al. | Jun 2006 | B1 |
7074373 | Warren et al. | Jul 2006 | B1 |
7077202 | Shaw et al. | Jul 2006 | B2 |
7100692 | Parsley et al. | Sep 2006 | B2 |
7118720 | Mendelsohn et al. | Oct 2006 | B1 |
7132183 | Galloway | Nov 2006 | B2 |
7168488 | Olsvik et al. | Jan 2007 | B2 |
7205448 | Gajda et al. | Apr 2007 | B2 |
7220502 | Galloway | May 2007 | B2 |
7299868 | Zapadinski | Nov 2007 | B2 |
7309383 | Beech, Jr. et al. | Dec 2007 | B2 |
7481275 | Olsvik et al. | Jan 2009 | B2 |
7666383 | Green | Feb 2010 | B2 |
7677309 | Shaw et al. | Mar 2010 | B2 |
7758663 | Rabovitser et al. | Jul 2010 | B2 |
7897126 | Rappas et al. | Mar 2011 | B2 |
7901644 | Rappas et al. | Mar 2011 | B2 |
7922782 | Sheth | Apr 2011 | B2 |
7926750 | Hauserman | Apr 2011 | B2 |
7976593 | Graham | Jul 2011 | B2 |
8021445 | Shaffer | Sep 2011 | B2 |
8114176 | Nahas | Feb 2012 | B2 |
8114177 | Hippo et al. | Feb 2012 | B2 |
8123827 | Robinson | Feb 2012 | B2 |
8163048 | Rappas et al. | Apr 2012 | B2 |
8192716 | Raman et al. | Jun 2012 | B2 |
8202913 | Robinson et al. | Jun 2012 | B2 |
8268899 | Robinson et al. | Sep 2012 | B2 |
8286901 | Rappas et al. | Oct 2012 | B2 |
8297542 | Rappas et al. | Oct 2012 | B2 |
8328890 | Reiling et al. | Dec 2012 | B2 |
8349037 | Steiner et al. | Jan 2013 | B2 |
8349039 | Robinson | Jan 2013 | B2 |
8361428 | Raman et al. | Jan 2013 | B2 |
8366795 | Raman et al. | Feb 2013 | B2 |
8479833 | Raman | Jul 2013 | B2 |
8479834 | Preston | Jul 2013 | B2 |
8502007 | Hippo et al. | Aug 2013 | B2 |
20020036086 | Minkkinen et al. | Mar 2002 | A1 |
20030070808 | Allison | Apr 2003 | A1 |
20030131582 | Anderson et al. | Jul 2003 | A1 |
20030167691 | Nahas | Sep 2003 | A1 |
20040020123 | Kimura et al. | Feb 2004 | A1 |
20040023086 | Su et al. | Feb 2004 | A1 |
20040123601 | Fan | Jul 2004 | A1 |
20040180971 | Inoue et al. | Sep 2004 | A1 |
20040256116 | Olsvik et al. | Dec 2004 | A1 |
20050107648 | Kimura et al. | May 2005 | A1 |
20050137442 | Gajda et al. | Jun 2005 | A1 |
20050192362 | Rodriguez et al. | Sep 2005 | A1 |
20050287056 | Baker et al. | Dec 2005 | A1 |
20050288537 | Maund et al. | Dec 2005 | A1 |
20060149423 | Barnicki et al. | Jul 2006 | A1 |
20060228290 | Green | Oct 2006 | A1 |
20060231252 | Shaw et al. | Oct 2006 | A1 |
20060265953 | Hobbs | Nov 2006 | A1 |
20060272813 | Olsvik et al. | Dec 2006 | A1 |
20070000177 | Hippo et al. | Jan 2007 | A1 |
20070051043 | Schingnitz | Mar 2007 | A1 |
20070083072 | Nahas | Apr 2007 | A1 |
20070180990 | Downs et al. | Aug 2007 | A1 |
20070186472 | Rabovitser et al. | Aug 2007 | A1 |
20070220810 | Leveson et al. | Sep 2007 | A1 |
20070227729 | Zubrin et al. | Oct 2007 | A1 |
20070237696 | Payton | Oct 2007 | A1 |
20070277437 | Sheth | Dec 2007 | A1 |
20070282018 | Jenkins | Dec 2007 | A1 |
20080022586 | Gilbert et al. | Jan 2008 | A1 |
20080141591 | Kohl | Jun 2008 | A1 |
20080289822 | Betzer Tsilevich | Nov 2008 | A1 |
20090012188 | Rojey et al. | Jan 2009 | A1 |
20090048476 | Rappas et al. | Feb 2009 | A1 |
20090090055 | Ohtsuka | Apr 2009 | A1 |
20090090056 | Ohtsuka | Apr 2009 | A1 |
20090165361 | Rappas et al. | Jul 2009 | A1 |
20090165376 | Lau et al. | Jul 2009 | A1 |
20090165379 | Rappas | Jul 2009 | A1 |
20090165380 | Lau et al. | Jul 2009 | A1 |
20090165381 | Robinson | Jul 2009 | A1 |
20090165382 | Rappas et al. | Jul 2009 | A1 |
20090165383 | Rappas et al. | Jul 2009 | A1 |
20090165384 | Lau et al. | Jul 2009 | A1 |
20090166588 | Spitz et al. | Jul 2009 | A1 |
20090169448 | Rappas et al. | Jul 2009 | A1 |
20090169449 | Rappas et al. | Jul 2009 | A1 |
20090170968 | Nahas et al. | Jul 2009 | A1 |
20090173079 | Wallace et al. | Jul 2009 | A1 |
20090217575 | Raman et al. | Sep 2009 | A1 |
20090217582 | May et al. | Sep 2009 | A1 |
20090217584 | Raman et al. | Sep 2009 | A1 |
20090217585 | Raman et al. | Sep 2009 | A1 |
20090217586 | Rappas et al. | Sep 2009 | A1 |
20090217587 | Raman et al. | Sep 2009 | A1 |
20090217588 | Hippo et al. | Sep 2009 | A1 |
20090217589 | Robinson | Sep 2009 | A1 |
20090217590 | Rappas et al. | Sep 2009 | A1 |
20090218424 | Hauserman | Sep 2009 | A1 |
20090220406 | Rahman | Sep 2009 | A1 |
20090229182 | Raman et al. | Sep 2009 | A1 |
20090235585 | Neels et al. | Sep 2009 | A1 |
20090236093 | Zubrin et al. | Sep 2009 | A1 |
20090246120 | Raman et al. | Oct 2009 | A1 |
20090259080 | Raman et al. | Oct 2009 | A1 |
20090260287 | Lau | Oct 2009 | A1 |
20090305093 | Biollaz et al. | Dec 2009 | A1 |
20090324458 | Robinson et al. | Dec 2009 | A1 |
20090324459 | Robinson et al. | Dec 2009 | A1 |
20090324460 | Robinson et al. | Dec 2009 | A1 |
20090324461 | Robinson et al. | Dec 2009 | A1 |
20090324462 | Robinson et al. | Dec 2009 | A1 |
20100005710 | Shaffer | Jan 2010 | A1 |
20100018113 | Bohlig et al. | Jan 2010 | A1 |
20100050654 | Chiu et al. | Mar 2010 | A1 |
20100071235 | Pan et al. | Mar 2010 | A1 |
20100071262 | Robinson et al. | Mar 2010 | A1 |
20100076235 | Reiling et al. | Mar 2010 | A1 |
20100120926 | Robinson et al. | May 2010 | A1 |
20100121125 | Hippo et al. | May 2010 | A1 |
20100159352 | Gelin et al. | Jun 2010 | A1 |
20100168494 | Rappas et al. | Jul 2010 | A1 |
20100168495 | Rappas et al. | Jul 2010 | A1 |
20100179232 | Robinson et al. | Jul 2010 | A1 |
20100287835 | Reiling et al. | Nov 2010 | A1 |
20100287836 | Robinson et al. | Nov 2010 | A1 |
20100292350 | Robinson et al. | Nov 2010 | A1 |
20110031439 | Sirdeshpande et al. | Feb 2011 | A1 |
20110062012 | Robinson | Mar 2011 | A1 |
20110062721 | Sirdeshpande et al. | Mar 2011 | A1 |
20110062722 | Sirdeshpande et al. | Mar 2011 | A1 |
20110064648 | Preston et al. | Mar 2011 | A1 |
20110088896 | Preston | Apr 2011 | A1 |
20110088897 | Raman | Apr 2011 | A1 |
20110146978 | Perlman | Jun 2011 | A1 |
20110146979 | Wallace | Jun 2011 | A1 |
20110197501 | Taulbee | Aug 2011 | A1 |
20110207002 | Powell et al. | Aug 2011 | A1 |
20110217602 | Sirdeshpande | Sep 2011 | A1 |
20110262323 | Rappas et al. | Oct 2011 | A1 |
20110294905 | Robinson et al. | Dec 2011 | A1 |
20120046510 | Sirdeshpande | Feb 2012 | A1 |
20120060417 | Raman et al. | Mar 2012 | A1 |
20120102836 | Raman et al. | May 2012 | A1 |
20120102837 | Raman et al. | May 2012 | A1 |
20120210635 | Edwards | Aug 2012 | A1 |
20120213680 | Rappas et al. | Aug 2012 | A1 |
20120271072 | Robinson et al. | Oct 2012 | A1 |
20120305848 | Sirdeshpande | Dec 2012 | A1 |
20130042824 | Sirdeshpande | Feb 2013 | A1 |
20130046124 | Sirdeshpande | Feb 2013 | A1 |
20130172640 | Robinson et al. | Jul 2013 | A1 |
Number | Date | Country |
---|---|---|
966660 | Apr 1975 | CA |
1003217 | Jan 1977 | CA |
1041553 | Oct 1978 | CA |
1106178 | Aug 1981 | CA |
1 125 026 | Jun 1982 | CA |
1187702 | Jun 1985 | CA |
1282243 | Apr 1991 | CA |
1299589 | Apr 1992 | CA |
1332108 | Sep 1994 | CA |
2673121 | Jun 2008 | CA |
2713642 | Jul 2009 | CA |
1477090 | Feb 2004 | CN |
101555420 | Oct 2009 | CN |
0024792 | Mar 1981 | EP |
0 067 580 | Dec 1982 | EP |
102828 | Mar 1984 | EP |
0 138 463 | Apr 1985 | EP |
0 225 146 | Jun 1987 | EP |
0 259 927 | Mar 1988 | EP |
0473153 | Mar 1992 | EP |
0 723 930 | Jul 1996 | EP |
819 | Apr 2000 | EP |
1001002 | May 2000 | EP |
1004746 | May 2000 | EP |
1136542 | Sep 2001 | EP |
1 207 132 | May 2002 | EP |
1768207 | Mar 2007 | EP |
2058471 | May 2009 | EP |
2 478 615 | Sep 1981 | FR |
2906879 | Apr 2008 | FR |
593910 | Oct 1947 | GB |
640907 | Aug 1950 | GB |
676615 | Jul 1952 | GB |
701 131 | Dec 1953 | GB |
760627 | Nov 1956 | GB |
798741 | Jul 1958 | GB |
820 257 | Sep 1959 | GB |
996327 | Jun 1965 | GB |
1033764 | Jun 1966 | GB |
1448562 | Sep 1976 | GB |
1453081 | Oct 1976 | GB |
1467219 | Mar 1977 | GB |
1467995 | Mar 1977 | GB |
1 599 932 | Jul 1977 | GB |
1560873 | Feb 1980 | GB |
2078251 | Jan 1982 | GB |
2154600 | Sep 1985 | GB |
2455864 | Jun 2009 | GB |
53-94305 | Aug 1978 | JP |
53-111302 | Sep 1978 | JP |
54020003 | Feb 1979 | JP |
54-150402 | Nov 1979 | JP |
55-12181 | Jan 1980 | JP |
56-145982 | Nov 1981 | JP |
56157493 | Dec 1981 | JP |
60-77938 | May 1985 | JP |
62241991 | Oct 1987 | JP |
62 257985 | Nov 1987 | JP |
03-115491 | May 1991 | JP |
2000290659 | Oct 2000 | JP |
2000290670 | Oct 2000 | JP |
2002105467 | Apr 2002 | JP |
2004292200 | Oct 2004 | JP |
2004298818 | Oct 2004 | JP |
2006 169476 | Jun 2006 | JP |
0018681 | Apr 2000 | WO |
0043468 | Jul 2000 | WO |
0240768 | May 2002 | WO |
02079355 | Oct 2002 | WO |
02103157 | Dec 2002 | WO |
03018958 | Mar 2003 | WO |
03033624 | Apr 2003 | WO |
2004055323 | Jul 2004 | WO |
2004072210 | Aug 2004 | WO |
2006031011 | Mar 2006 | WO |
2007005284 | Jan 2007 | WO |
2007047210 | Apr 2007 | WO |
2007068682 | Jun 2007 | WO |
2007076363 | Jul 2007 | WO |
2007077137 | Jul 2007 | WO |
2007077138 | Jul 2007 | WO |
2007083072 | Jul 2007 | WO |
2007128370 | Nov 2007 | WO |
2007143376 | Dec 2007 | WO |
2008058636 | May 2008 | WO |
2008073889 | Jun 2008 | WO |
2008087154 | Jul 2008 | WO |
2009018053 | Feb 2009 | WO |
2009048723 | Apr 2009 | WO |
2009048724 | Apr 2009 | WO |
2009086361 | Jul 2009 | WO |
2009086362 | Jul 2009 | WO |
2009086363 | Jul 2009 | WO |
2009086366 | Jul 2009 | WO |
2009086367 | Jul 2009 | WO |
2009086370 | Jul 2009 | WO |
2009086372 | Jul 2009 | WO |
2009086374 | Jul 2009 | WO |
2009086377 | Jul 2009 | WO |
2009086383 | Jul 2009 | WO |
2009086407 | Jul 2009 | WO |
2009086408 | Jul 2009 | WO |
2009111330 | Sep 2009 | WO |
2009111331 | Sep 2009 | WO |
2009111332 | Sep 2009 | WO |
2009111335 | Sep 2009 | WO |
2009111342 | Sep 2009 | WO |
2009111345 | Sep 2009 | WO |
2009124017 | Oct 2009 | WO |
2009124019 | Oct 2009 | WO |
2009158576 | Dec 2009 | WO |
2009158579 | Dec 2009 | WO |
2009158580 | Dec 2009 | WO |
2009158582 | Dec 2009 | WO |
2009158583 | Dec 2009 | WO |
2010033846 | Mar 2010 | WO |
2010033848 | Mar 2010 | WO |
2010033850 | Mar 2010 | WO |
2010033852 | Mar 2010 | WO |
2010048493 | Apr 2010 | WO |
2010078297 | Jul 2010 | WO |
2010078298 | Jul 2010 | WO |
2010132549 | Nov 2010 | WO |
2010132551 | Nov 2010 | WO |
2011017630 | Feb 2011 | WO |
2011029278 | Mar 2011 | WO |
2011029282 | Mar 2011 | WO |
2011029283 | Mar 2011 | WO |
2011029284 | Mar 2011 | WO |
2011029285 | Mar 2011 | WO |
2011034888 | Mar 2011 | WO |
2011034889 | Mar 2011 | WO |
2011034890 | Mar 2011 | WO |
2011034891 | Mar 2011 | WO |
2011049858 | Apr 2011 | WO |
2011049861 | Apr 2011 | WO |
2011063608 | Jun 2011 | WO |
2011084580 | Jul 2011 | WO |
2011084581 | Jul 2011 | WO |
2011106285 | Sep 2011 | WO |
2011139694 | Nov 2011 | WO |
2011150217 | Dec 2011 | WO |
2012024369 | Feb 2012 | WO |
2012033997 | Mar 2012 | WO |
2012061235 | May 2012 | WO |
2012061238 | May 2012 | WO |
2012116003 | Aug 2012 | WO |
2012145497 | Oct 2012 | WO |
2012166879 | Dec 2012 | WO |
2013025808 | Feb 2013 | WO |
2013025812 | Feb 2013 | WO |
2013052553 | Apr 2013 | WO |
Entry |
---|
U.S. Appl. No. 12/778,538, filed May 12, 2010, Robinson, et al. |
U.S. Appl. No. 12/778,548, filed May 12, 2010, Robinson, et al. |
U.S. Appl. No. 12/778,552, filed May 12, 2010, Robinson, et al. |
Asami, K., et al., “Highly Active Iron Catalysts from Ferric Chloride or the Steam Gasification of Brown Coal,” ind. Eng. Chem. Res., vol. 32, No. 8, 1993, pp. 1631-1636. |
Berger, R., et al., “High Temperature CO2-Absorption: A Process Offering New Prospects in Fuel Chemistry,” The Fifth International Symposium on Coal Combustion, Nov. 2003, Nanjing, China, pp. 547-549. |
Brown et al., “Biomass-Derived Hydrogen From a Thermally Ballasted Gasifier,” Aug. 2005. |
Brown et al., “Biomass-Derived Hydrogen From a Thermally Ballasted Gasifier,” DOE Hydrogen Program Contractors' Review Metting, Center for Sustainable Environmental Technologies, Iowa State University, May 21, 2003. |
Cohen, S.J., Project Manager, “Large Pilot Plant Alternatives for Scaleup of the Catalytic Coal Gasification Process,” FE-2480-20, U.S. Dept. of Energy, Contract No., EX-76-C-01-2480, 1979. |
Euker, Jr., C.A., Reitz, R.A., Program Managers, “Exxon Catalytic Coal-Gasification-Process Development Program,” Exxon Research & Engineering Company, FE-2777-31, U.S. Dept. of Energy, Contract No. ET-78-C-01-2777, 1981. |
Kalina, T., Nahas, N.C., Project Managers, “Exxon Catalaytic Coal Gasification Process Predevelopment Program,” Exxon Research & Engineering Company, FE-2369-24, U.S. Dept. of Energy, Contract No., E(49-18)-2369, 1978. |
Nahas, N.C., “Exxon Catalytic Coal Gasification Process—Fundamentals to Flowsheets,” Fuel, vol. 62, No. 2, 1983, pp. 239-241. |
Ohtsuka, Y. et al., “Highly Active Catalysts from Inexpensive Raw Materials for Coal Gasification,” Catalysis Today, vol. 39, 1997, pp. 111-125. |
Ohtsuka, Yasuo et al, “Steam Gasification of Low-Rank Coals with a Chlorine-Free Iron Catalyst from Ferric Chloride,” Ind. Eng. Chem. Res., vol. 30, No. 8, 1991, pp. 1921-1926. |
Ohtsuka, Yasuo et al., “Calcium Catalysed Steam Gasification of Yalourn Brown Coal,” Fuel, vol. 65, 1986, pp. 1653-1657. |
Ohtsuka, Yasuo, et al, “Iron-Catalyzed Gasification of Brown Coal at Low Temperatures,” Energy & Fuels, vol. 1, No. 1, 1987, pp. 32-36. |
Ohtsuka, Yasuo, et al., “Ion-Exchanged Calcium From Calcium Carbonate and Low-Rank Coals: High Catalytic Activity in Steam Gasification,” Energy & Fuels 1996, 10, pp. 431-435. |
Ohtsuka, Yasuo et al., “Steam Gasification of Coals with Calcium Hydroxide,” Energy & Fuels, vol. 9, No. 6, 1995, pp. 1038-1042. |
Pereira, P., et al., “Catalytic Steam Gasification of Coals,” Energy & Fuels, vol. 6, No. 4, 1992, pp. 407-410. |
Ruan Xiang-Quan, et al., “Effects of Catalysis on Gasification of Tatong Coal Char,” Fuel, vol. 66, Apr. 1987, pp. 568-571. |
Tandon, D., “Low Temperature and Elevated Pressure Steam Gasification of Illinois Coal,” College of Engineering in the Graduate School, Southern Illinois university at Carbondale, Jun. 1996. |
Adsorption, http://en.wikipedia.org/wiki/Adsorption, pp. 1-8 (Oct. 17, 2007). |
Amine gas treating, http://en.wikipedia.org/wiki/Acid—gas—removal, pp. 1-4 (Oct. 21, 2007). |
Coal, http://en.wikpedia.org/wiki/Coal—gasification, pp. 1-8 (Oct. 29, 2007). |
Coal Data: A Reference, Energy Information Administration, Office of Coal, Nuclear, Electric, and Alternate Fuels U.S. Department of Energy, DOE/EIA-0064(93), Feb. 1995. |
Deepak Tandon, Dissertation Approval, “Low Temperature and Elevated Pressure Steam Gasification of Illinois Coal”, Jun. 13, 1996. |
Demibras, “Demineralization of Agricultural Residues by Water Leaching”, Energy Sources, vol. 25, pp. 679-687, (2003). |
Fluidized Bed Gasifiers, http://www.energyproducts.com/fluidized—bed—gasifiers.htm, Oct. 2007, pp. 1-5. |
Gas separation, http://en.wikipedia.org/wiki/Gas—separation, pp. 1-2 (Feb. 24, 2007). |
Gasification, http://en.wikipedia.org/wiki/Gasification, pp. 1-6 (Oct. 29, 2007). |
Gallagher Jr., et al., “Catalytic Coal Gasification for SNG Manufacture”, Energy Research, vol. 4, pp. 137-147, (1980). |
Heinemann, et al., “Fundamental and Exploratory Studies of Catalytic Steam Gasification of Carbonaceous Materials”, Final Report Fiscal Years 1985-1994. |
Jensen, et al. Removal of K and C1 by leaching of straw char, Biomass and Bioenergy, vol. 20, pp. 447-457, (2001). |
Mengjie, et al., “A potential renewable energy resource development and utilization of biomass energy”, http://www.fao.org.docrep/T4470E/t4470e0n.htm, pp. 1-8 (1994). |
Meyers, et al. Fly Ash as a Construction Material for Highways, A Manual. Federal Highway Administration, Report No. FHWA-IP-76-16, Washington, DC, 1976. |
Moulton, Lyle K. “Bottom Ash and Boiler Slag”, Proceedings of the Third International Ash Utilization Symposium, U.S. Bureau of Mines, Information Circular No. 8640, Washington, DC, 1973. |
Natural gas processing, http://en.wikipedia.org/wiki/Natural—gas—processing, pp. 1-4 (Oct. 22, 2007). |
Natural Gas Processing: The Crucial Link Between Natural Gas Production and Its Transportation to Market. Energy Information Administration, Office of Oil and Gas; pp. 1-11, (2006). |
Prins, et al., “Exergetic optimisation of a production process of Fischer-Tropsch fuels from biomass”, Fuel Processing Technology, vol. 86, pp. 375-389, (2004). |
Reboiler, http://en.wikipedia.org/wiki/Reboiler, pp. 1-4 (Nov. 11, 2007). |
What is XPS?, http://www.nuance.northwestern.edu/KeckII/xps1.asp, 2006, pp. 1-2 (2006). |
2.3 Types of gasifiers, http://www.fao.org/docrep/t0512e/T0512e0a.htm, pp. 1-6 (1986). |
2.4 Gasification fuels, http://www.fao.org/t0512e0/T0512e0b.htm#TopofPage, pp. 1-8 (1986). |
2.5 Design of downdraught gasifiers, http://www.fao.org/docrep/t0512e/T0512e0c.htm#TopOfPage, pp. 1-8 (1986). |
2.6 Gas cleaning and cooling, http://www.fao.org/docrep/t0512e0d.htm#TopOfPage, pp. 1-3 (1986). |
A.G. Collot et al., “Co-pyrolysis and co-gasification of coal and biomass in bench-scale fixed-bed and fluidized bed reactors”, (1999) Fuel 78, pp. 667-679. |
Wenkui Zhu et al. “Catalytic gasfcation of char fom co-pyrolysis of coal and biomass”, (2008) Fuel Processing Technology, vol. 89, pp. 890-896. |
Chiesa P. et al., “Co-Production of hydrogen, electricity and C02 from coal with commercially ready technology. Part A: Performance and emissions”, (2005) International Journal of Hydrogen Energy, vol. 30, No. 7, pp. 747-767. |
Chiaramonte et al, “Upgrade Coke by Gasification”, (1982) Hydrocarbon Processing, vol. 61 (9), pp. 255-257 (Abstract only). |
Gerdes, Kristin, et al., “Integrated Gasification Fuel Cell Performance and Cost Assessment,” National Energy Technology Laboratory, U.S. Department of Energy, Mar. 27, 2009, pp. 1-26. |
Ghosh, S., et al., “Energy Analysis of a Cogeneration Plant Using Coal Gasification and Solid Oxide Fuel Cell,” Energy, 2006, vol. 31, No. 2-3, pp. 345-363. |
Jeon, S.K., et al., “Characteristics of Steam Hydrogasification of Wood Using a Micro-Batch Reactor,” Fuel, 2007, vol. 86, pp. 2817-2823. |
Li, Mu, et al., “Design of Highly Efficient Coal-Based Integrated Gasification Fuel Cell Power Plants,” Journal of Power Sources, 2010, vol. 195, pp. 5707-5718. |
Prins, M.J., et al., “Exergetic Optimisation of a Production Process of Fischer-Tropsch Fuels from Biomass,” Fuel Processing Technology, 2005, vol. 86, No. 4, pp. 375-389. |
Hydromethanation Process, GreatPoint Energy, Inc., from World Wide Web <http://greatpointenergy.com/ourtechnology.php.> accessed Sep. 5, 2013. |
Sigma-Aldrich “Particle Size Conversion Table” (2004); from World Wide Web <http:/www.sigmaaldrich.com/chemistry/learning-center/technical-library/particle-size-conversion.printerview.html>. |
Number | Date | Country | |
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20140090584 A1 | Apr 2014 | US |
Number | Date | Country | |
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61708104 | Oct 2012 | US | |
61775771 | Mar 2013 | US | |
61815800 | Apr 2013 | US |