The present invention is related to a gasification process, and in particular, to a gasification process having at least one endothermic reduction zone sandwiched between at least two high-temperature oxidation zones.
The production of clean syngas and complete fuel conversion are the primary requirements for successful gasification of carbonaceous fuels for commercial applications such as production of heat, electricity, gaseous as well as liquid fuels, and chemicals. These requirements are critical to achieving desired process economics and favorable environmental impact from fuel conversion at scales ranging from small distributed- to large-scale gasification-based processes.
Among the commonly known gasifier types defined based on bed configurations (fixed bed, fluidized bed, and entrained bed) and their variants, the downdraft fixed-bed gasifier is known to produce the lowest tar in hot syngas attributed primarily to the bed configuration in which the evaporation and devolatilized or pyrolyzed products are allowed to pass through a high-temperature oxidation zone such that long-chain hydrocarbons are reduced to their short-chain constituents and these gaseous combustion and reduced-pyrolysis products react with unconverted carbon or char in the reduction zone to produce clean syngas.
The conversions occurring in Zone 1 are primarily endothermic, and the volatile yields are dependent on the heating rate, which is dependent on fuel particle size and temperature. The reduction reactions occurring in Zone 3 are predominantly endothermic. These reactions are a strong function of temperature and determine fuel conversion rate, thus defining fuel throughput, syngas production rate, and syngas composition.
The heat required to sustain the endothermic reactions in the reduction zone is transferred from the single oxidation zone. Thus production of clean syngas and the extent of carbon conversion heavily depend on the temperature and heat transfer from the oxidation zone to the reduction zone. As shown in
The critical factors of size, location, and temperature of the oxidation zone severely restrict the range of carbonaceous fuel that can be utilized in the same gasifier, which is typically designed to convert fuels with a narrow range of physicochemical characteristics, particularly particle size, chemical composition, and moisture content (e.g., typical fuel specifications for commercial biomass gasifier includes chipped wood containing less than 15% moisture and less than 5% fines). Any variation in these fuel characteristics is known to have adverse impacts on gasifier performance, and such fuels are, therefore, either preprocessed (such as moisture and fines reduction using dryer) and/or are restricted from conversion under applicable gasification technology warranty agreements.
As such, the current state of gasifier design and the inability of heretofor gasifiers to maintain a temperature profile required in gasifier zones because of the dual impact of size and temperature reduction of the critical oxidation zone, caused when fuels containing high moisture, high volatiles, or a large fraction of fine particles or fuels having low reactivity when gasified is an undesirable shortcoming of current gasifier technology. In addition, gasification of such fuels results in partial decomposition of the pyrolysis product causing undesirably high concentrations of tar in the syngas as well as adversely affecting its composition and char conversion rate, a combined effect of inadequate temperature in the kinetically controlled reduction zone. Therefore, a gasification process and/or a gasifier that can provide a long, uniform temperature zone in the gasifier, regardless of the above-referenced variations in fuel composition, would be desirable.
The present invention discloses a gasifier and/or a gasification process that provides a long, uniform temperature zone in the gasifier, regardless of the particle size, chemical composition, and moisture content of the fuel. As a result, any carbonaceous fuel containing high moisture and/or high volatiles can be used as a potential gasification feedstock while maintaining a desired low tar composition of syngas. The gasifier and/or gasification process also addresses one of the major limitations of maximum allowable throughput in a fixed-bed configuration imposed by the geometric restriction of penetration of the oxidizer in the reacting bed for maintaining uniform temperature and fuel conversion profiles.
The gasifier and/or gasification process sandwiches one or multiple reduction zones between two or more oxidation zones, and affords flow of product gases through these zones such that precise control over temperature and fuel conversion profiles can be achieved.
Nomenclature
As used herein, conventional carbonaceous fuels are those in which the combustion process is known or carried out for energy recovery. Such fuels are generally classified as biomass or coal.
As used herein, nonconventional carbonaceous fuels are typically industrial or automotive wastes having a complex composition such that their conversion requires a nontypical method of feeding or injection, residue extraction, devolatilization process control, and devolatilized product distribution for effective gasification or destruction of toxic organic compounds by maintaining aggressive gasification conditions achieved by supplemental fuel or catalysts. Such fuels include whole automotive tires consisting of steel wires and carbon black, structural plastics material clad with metal or inert material, contaminated waste material requiring aggressive gasification conditions, printed circuit boards, waste fuel, heavy-organic-residue sludges, and highly viscous industrial effluents from the food and chemical industries.
As used herein, primary fuel is the largest fraction of the conventional and nonconventional fuels injected upstream of the oxidation zone (OX-1) in the zone defined as ED-1, ED-2, etc. (discussed in greater detail below with reference to
As used herein, secondary fuel is the small or minor fuel fraction formed within the gasification process (e.g., combustible fuel formed in the syngas cleanup system) and cogasified for the purpose of improving syngas composition. These fuels are injected/coinjected with primary fuels and/or injected separately in the primary gasification zones (evaporation and devolatilization, oxidation, and reduction zones) with or without the help of an oxidizer or carrier gas and with the help of a dedicated fuel injection system.
As used herein, auxiliary fuel is defined as fuel other than the primary and secondary fuels and includes syngas and injectable fuels that can support stable combustion.
As used herein, oxidizer is defined as the substance that reacts with the primary and secondary fuels in at least two oxidation zones. One or more types of oxidizer can be simultaneously used in pure or mixed forms. Pure oxidizers include air, oxygen, steam, peroxides, ammonium perchlorate, etc.
As used herein, mixed-reaction (MR) mode is a process in which at least two types of bed are formed in a single gasifier in order to facilitate fuel conversion, e.g., fuel with a large fraction of fines and friable char (or low-crushing-strength material) is injected into a packed-bed configuration; however, after passing through the ED-1 and OX-1 zones, the friable material is subjected to enough crushing force such that its particle size is reduced or can be easily broken by mechanical crushing. It is possible to inject such fine fuel in the MR zone (like oxidation-2 and RD-1 in
The invention aims to convert carbonaceous fuel or a mixture of carbonaceous and noncarbonaceous material into a combustible mixture of gases referred to as syngas. Since the chemical conversion occurs as a result of heat, the process is commonly known as the thermochemical conversion process. Thus the aim of the process is to convert (or recover) the chemical energy of the original material into the chemical energy of syngas. The required process heat is either fully or partially produced by utilizing primarily the chemical energy of the original fuel. The invention allows the injection of heat from an auxiliary source either through direct heat transfer (heat carrier fluid injection, e.g., steam, hot air, etc.) or indirectly into the reaction zones. The primary embodiments of the invention are to maximize the gasification efficiency and flexibility of the conversion process.
The choice of oxidizer/gasification medium in one or more of the gasifier zones located near the exit plane of the gasifier can provide selective heating of the inorganic residue to high temperatures (1450°-1600° C.) at which ash vitrification can occur. The sandwich configuration can favorably utilize char (supplemented by syngas as fuel if necessary) in a simple self-sustaining thermal process without requiring high-grade electricity typically used in thermodynamically unfavorably plasma- or arc-based heating processes, a unique feature for attaining high conversion efficiency.
One of the major issues faced in conventional gasification processes is the difficulty of attaining complete carbon conversion of low-reactivity fuels. The char in such a process is typically extracted from the gasifier and either disposed of or oxidized in a separate furnace system. A similar arrangement for carbon conversion is also provided in the case of a solid fuel (biomass, coal, and black liquor) fluidized-bed steam reformer for the production of hydrogen-rich syngas. Because of the predominantly occurring water-gas shift reaction, the concentration of CO2 in syngas is high, along with very high concentrations of unconverted tar. The sandwich gasification process overcomes the difficulties found in prior art gasification processes and attains clean, hydrogen-rich, low-CO2 syngas by effectively utilizing carbon/char in situ to provide temperatures favorable for Boudouard reactions. The unreactive char is converted in the mixed-mode gasification zone of the sandwich configuration involving the entrained- and/or fluidized-bed zone formed by the hydrodynamics of the fine char and gasification medium or oxidizer.
The basis of the invention is explained with the help of results from equilibrium calculations conducted to determine the effect of parametric variations on fuel conversion using model fuels such as biomass (pine wood) of varying moisture content (0%-60%), biomass char (carbonaceous residue obtained from the gasifier), and an oxidizer such as air and 10% enriched-oxygen air.
ERs ranging from 0.7 to 1.0 and greater than 1 are identified as fuel-rich and fuel-lean combustion zones, respectively. The gasification range ER (0-0.7) is typically intended for production of syngas containing a major fraction of the chemical energy of the original fuel. The chemical energy is completely converted to sensible heat at stoichiometric (or ER=1), or fuel-lean, combustion. Fuel-rich combustion is primarily intended to achieve stable combustion producing manageable low-temperature product gases compared to the highest possible temperature achieved near stoichiometric conditions. A small fraction of the unconverted chemical energy in the gas is released in the secondary-stage oxidation process. As required in most combustion applications, the fuel-lean condition is aimed at attaining low-temperature product gas, achieved as a result of the dilution effect of the oxidizer.
The plot in
The plots in
The gasifiers used in practice are designed primarily to achieve the highest possible conversion of carbon. Since the adiabatic condition is difficult to achieve because of the inevitable heat losses from the gasifier, the operating temperatures are typically lower than the AFT. As a result, the unconverted char fraction is higher, even at intermediate ER operating range. This volatile, depleted residue (or char) is typically removed from the gasifier. Since the reactivity of such char decreases after exposure to atmospheric nitrogen, the value of such char as a fuel is low, and thus it becomes a disposal liability. This further limits the operating regimes of the ER and operable moisture content in the fuel. Fuels with a lower AFT at an intermediate range ER (such as in the case of high-moisture biomass) are operated at a high range ER, although at the cost of syngas chemical energy, thus lowering the concentration of H2 and CO (see
The embodiment of the sandwich gasification process is to overcome the above-stated limitations by staging the operating ER in multiple sandwiching zones and establishing corresponding equilibrium conditions by creating high-temperature conditions within the single reactor by in situ conversion of the fuel residue or char normally removed from the conventional gasifier. The effectiveness of char and the approach to the sandwiching are discussed as follows.
In order to achieve different ER and corresponding equilibrium conditions in the gasifier, the oxidizer distribution could be achieved such that a number of sandwiching zones are arranged in series and/or parallel in the reactor, as shown in
The ability to transfer heat in the reacting bed (as discussed above) by creating a large temperature gradient within the reacting bed as a result of sandwiching reaction zones is one of the main embodiments of the invention. The example of attaining higher chemical energy by virtue of sandwiching two gasification zones, causing an effective increase in reaction zone temperature, is shown in
The fuel conversion process in the sandwich gasifier invention occurs in three types of primary zones and four types of secondary zones arranged in a characteristic pattern such that it facilitates complete conversion into the desired composition of clean syngas and residue. The primary zones are designated as: (1) evaporation and devolatilization zone (ED); (2) oxidation zone (OX); (3) and reduction zone (RD), whereas the secondary zones are designated as: (1) fuel injection zone (INJF); (2) oxidizer injection zone (INJOX); (3) syngas extraction zone (SGX); and (4) residue extraction zone (RX),
The role of the primary zones is to thermochemically decompose complex fuel into energy-carrying gaseous molecules, while the role of the secondary zones is to transport the reactant and product in and out of these zones. The reacting bed configuration is either a fixed bed or a combination of fixed, fluidized, and entrained bed, referred to as an MR bed or zone, as shown in
Gasifier Operating Conditions and Configuration
The gasifier is operated under negative (or subatmospheric), atmospheric, or positive pressure, depending on the fuel and syngas applications. The operating temperature of individual reacting zones depends on the fuel type, extent of inert residue requirements, type of oxidizer, and operating ER, and it is independent of the operating pressure. The fuel and oxidizer injection method is dependent on the operating pressure of the gasifier.
The primary embodiment includes a gasifier of open-port and closed-port configurations as shown in
The two oxidizing or gasifying media injected from two sides of the oxidation zones (Zone 2a and 2b) in the proposed sandwich gasification process can be distinctly different or the same and can be multicomponent or single component, depending on the syngas composition requirement. For example, the gasifying medium can be air or a mixture of enriched-oxygen air and steam or pure oxygen and steam. In the case where steam is the gasifying medium injected from the Zone 2a side, the high-temperature oxidation Zone 2a is replaced by an indirectly heated zone satisfying all of its functional requirements (heat for pyrolysis and for the reduction zone), and Zone 2b is sustained to achieve complete carbon conversion.
The residual ash is removed at the downstream of Zone 2b with the help of a dry or wet ash removal system. The fraction of entrained ash is removed with the help of a cyclone or particulate filter system provided in the path of syngas and removed separately. Depending on the temperature in Zone 2b, the dry or molten ash may be extracted downstream of the char oxidation Zone 2b, depending on the required amount of inorganics and their composition present in the feedstock being gasified. This is one of the characteristics of the sandwich gasification process in which molten ash can be recovered while achieving the higher-efficiency benefit of the low-temperature gasification process.
The open-port configuration is allowed strictly under negative pressure operating conditions such that primary fuel and oxidizers or only oxidizers are injected from ports open to the atmosphere, and the flow direction of the reactant is facing the gasifier (positive) or as a net suction effect (negative pressure) created by one or many devices such as aerodynamic (blower or suction fan and/or ejector) or hydrodynamic (hydraulics ejector) devices and/or devices like an internal combustion engine creating suction. During normal operating conditions of the gasifier, including start-up and shutdown, negative pressure ensures proper material flow in the gasifier and that products are removed from designated extraction zones. The backflow of the gases is prevented by providing physical resistance in addition to maintaining enough negative pressure within the gasifier. The embodiment includes an open-port gasifier that also allows fuel injection with the help of an enclosed hopper or fuel storage device from which the fuel is continuously or intermittently fed to the gasifier (e.g., by enclosed screw, belt, bucket elevator, pneumatic pressure feed system feed, etc.) while the oxidizer is injected with the help of a mechanical or hydrodynamically driven pump (e.g., compressor, twin fluid ejectors, etc.).
The embodiment of the gasifier includes a closed-port gasifier in which the reactants (oxidizers and fuel streams) are injected in a pressurized (higher-than-atmospheric-pressure) gasifier. The fuel is injected from a conventional lock hopper maintained at pressure equilibrated with the gasifier. The oxidizers are injected at pressures higher than gasifier operating pressure. The gas flow in and out of the gasifier is thus maintained by positive pressure. A suction device may be used in order to maintain higher gasifier throughput at low positive operating pressures. In both configurations, the reactant injection is continuous in order to maintain the location of the gasification zones and steady-state production of syngas.
Gasifier Primary Zones
The arrangement of the primary zones and the characteristic operating features are described in the following section.
The ED zone is typically located downstream of the fuel injection zone. There is at least one ED zone in the sandwich gasifier. The primary processes occurring in this zone are evaporation and devolatilization. Within this zone, the occurrence of these processes is either simultaneous or in sequence, depending on fuel size and characteristics. The overall process is endothermic, and the required heat is supplied by the hot reactant and/or fuel combustion products, conduction, and radiation from the interfacing high-temperature oxidation zone. This zone interfaces with at least one oxidation zone, as shown in
The case of multiple fuel gasification processes injected separately as primary fuels in the gasifier from different sections in the gasifier but sharing the exothermic heat profile of the hot oxidization zones is shown in
The combustible residue is injected in the primary zone (CX-2,
The process provides the flexibility of utilizing another primary fuel (ED-1 zone) to improve gasification efficiency and produce clean syngas in the case of fuels lacking in residue (e.g., plastics containing near 100% volatiles, requiring conversion over a catalytic carbon bed). The feature allows utilization of an inert bed or catalyst bed sandwiched between oxidation zones for attaining uniform temperature in the reacting bed consisting of inert solids. As shown in
The OX zone is characteristically a high-temperature zone where the oxidative reaction between the primary and secondary fuels and/or devolatilized products from these fuels (volatiles and char) and oxidizing gasification medium occurs. There is at least one OX zone that interfaces with at least one ED zone, and there are at least two OX zones interfacing with at least one reduction (RD) zone (described in the following text) characterizing the present invention. The primary purpose of these zones is to maintain an exothermic heat profile necessary to sustain endothermic reactions in the RD and ED zones.
The distinct difference between the OX-1 and other oxidation zones such as OX-2 and OX-3 (shown in
In the case of low ER operating mode (ER ranging from near zero to 0.25, with low AFTs but high chemical energy; see
Reduction (RD) zone is sandwiched between the oxidation zones, as shown in
Two examples of different fuels are considered to explain this process as follows.
Example 1 is the conversion of coal and biomass at atmospheric conditions with air the gasification medium, with two reduction and three oxidation zones (see
Example 2, the conversion of plastics (in ED-2) with biomass (in ED-1) as the primary fuel and air as the gasification medium as well as a volatile carrier from ED-2 to ED-1, will achieve conditions similar to Example
1.
Fuel Injection
The gasification of one or multiple fuel streams is achieved in the same gasifier. The stream of the largest weight fraction of the fuels injected is defined as the primary fuel, and the other smaller fuel stream is defined as the secondary fuel stream.
The primary fuel is gravity and/or mechanically and/or aerodynamically (see definition) force-fed from at least one port located on the top of the gasifier in a top-down injection mode (see
The secondary, or minor, fuel is injected by gravity and/or mechanically and/or aerodynamically from the same and/or different port utilized for primary fuel injection. In addition, the secondary fuel can be injected directly into one or more conversion zones in order to augment the conversion of both the primary as well as the secondary fuel streams.
Depending on the gasifier operating pressure, the pressure in the feed section is equilibrated with the fuel injection chamber with the gasification fluid in order to prevent a reverse-flow situation.
The gasifier can convert fuel of complex shapes and/or liquid and gaseous fuel of all rheological properties. In order to utilize off-the-shelf fuel storage and feed systems, large fuel units are broken down to a small size with the help of conventional equipment. The sized fuel is injected as described above and shown in
Oxidizer Injection
The gasifier invention consists of at least two distinct oxidation zones separated by at least one reduction zone. In the gasifier, there is at least one oxidation zone that interfaces with a devolatilization zone named as “OX-1,” as shown in
The oxidizer is preheated in an external heat exchanger to a temperature ranging from 100° to 600° C. prior to its injection. The hot oxidiser injected through INJOX-1A helps to uniformly preheat the fuel bed, transporting devolatilized product produced in ED-1 to the oxidation zone and achieving partial premixing of the fuel and oxidizer prior to the OX-1. In the case of large-sized fuel injected as the second primary fuel in zone INJF-2, the devolatilized product from the annular space or chamber formed around the gasifier is injected in the gasifier with the help of an oxidizer or a carrier gas injected from zone INJOX-1C, as shown in
Oxidizer injection from INJOX-1B is to stabilize the location of the oxidation zone and achieve uniform distribution in the reaction zone. The oxidizer is fed from the primary fuel-feeding zone end of the gasifier and injected at the desired point of transition between ED-1 and OX-1 with the help of multiple submerged (into fuel bed) or embedded lance inserted along the axis of the gasifier, as shown in
The lance are made from two pipes or cones forming sealed annular space for the flow of oxidizer into the injection zone INJOX-1B and allowing solid flow through the hollow middle section. The oxidizer flows within the annular space of the lance extended up to the oxidizer injection zones. This arrangement is aimed at providing adequate heat-transfer surface area to uniformly heat the fuel bed in order to restrict the fuel flow cross-sectional area in the case of a high-fuel-throughput gasifier having an outer shell diameter greater than 4 ft. In order to augment heat transfer in the evaporation and devolatilization zone, lean combustion of auxiliary fuel is achieved within the enclosed annular space of the lance. The heated lance surface achieves indirect heat transfer while the oxidizer-rich hot product gases provide direct heat transfer. The functions of lance are summarized as follows:
The oxidizer injection in the OX-2 and OX-3 zones (and could be OX-3, OX-4, OX-n) sandwiched with RD-1 and RD-2, respectively, as shown in
In order to achieve the MR mode of operation (see definition of MR in the nomenclature), the oxidizer is injected from the grate or distributor plate such that the desired hydrodynamics in the bed (fluidized bed or entrained bed) are achieved. The expanded view of the MR zone is shown in
As an alternative to the lance injection system, a fixed-grate or moving-grate system is used, as shown in
Extraction Zone
The syngas, char, and inert residue are extracted from this zone and are represented by SGX-n, CX-n, and RX-n, respectively, where “n” is the number of the zone which is 1 or greater than 1.
The SGX zone is located in the reduction zone and is one of the primary embodiments of the invention. The extraction is caused under the flow condition created by negative differential pressure created in the direction of the flow under both high- and low-pressure conditions. Tar reduction in the active and hot char zones sandwiched between hot oxidation zones is one of the major benefits of extraction from the reduction zone. There is one or multiple uniformly sized and symmetrically distributed extraction ports located in the reduction zone sandwiched by two distinct oxidation zones. In the case of a gasifier with more than one reduction zone, the syngas is extracted from one or multiple extraction zones distinctly located in the respective zones.
The location and configuration of the extraction ports is such that the major fraction of the syngas reverses the flow direction. Such flow rectification is intended to minimize in situ particulate entrainment in the gasifier.
In the case of a low-throughput gasifier, the SGX port is located on the inside gasifier wall where the reduction zone is located, as shown in
Char (CX) and inert residue (RX) extraction in the current invention occurs from two distinct gasifier zones such that the desired material is extracted at required rates. This is shown in
The inert residue from the gasifier is extracted from zone RX such that the combustible fraction in the material (mostly carbon) is near zero. This is achieved because residue passes through the hottest zone created by the oxidation of char in a counterflow arrangement. Under steady-state operation, the fuel injection and inert residue extraction rates are maintained such that inert mass balance across the gasifier is achieved.
The embodiment of the research allows precise control in achieving this balance since the oxidizer type and its injection rate in the counterflow mode is easily achieved. In the special case where char reactivity is low as a result of the physicochemical composition of the fuel or reduces as a result of residence time and/or temperature, high ER oxidation can be achieved in the RX zone such that complete conversion is achieved. The injection of OEA or pure oxygen can attain the required temperature in the oxidation zone closest to the RX zone. Depending on the ash fusion temperature, the extraction process is adopted for extracting solid or molten liquid. The hot gaseous products from such a high ER zone are injected in the reduction zones to take advantage of direct heat transfer necessary to promote kinetics in these zones by increasing the temperature, as described earlier.
The embodiment includes activation of char by staged injection of oxidizers in the zones interfacing with RX zone. The inert residue extraction is replaced by activated char extraction and is referred to as ACRX zone (not shown in the figure). The extraction of char from the CX zone is either combined or maintained separately.
Referring now to
It is appreciated that the oxidation zone Ox-2 in the sandwich mode can achieve complete carbon conversion unlike typical downdraft gasifiers that require unconverted carbon removal from the low-temperature frozen reaction zone. As such, near-zero carbon and tar conversion in the sandwich gasifier showed high-efficiency gasification of all test fuels. For example, the turkey waste had more than 50% inert matter (43% moisture and 13% inorganics) and yet a self-sustained gasification efficiency was achieved in the sandwich gasifier between 75% and 80% which was much higher than in the typical downdraft gasifier mode. In fact, experiments in typical gasifier mode did not sustain conversion due to the high inert content in the turkey waste.
In view of the teaching presented herein, it is to be understood that numerous modifications and variations of the present invention will be readily apparent to those of skill in the art. The foregoing is illustrative of specific embodiments of the invention but is not meant to be a limitation upon the practice thereof. As such, the application is to be interpreted broadly.
This application claims priority to U.S. Provisional Patent Application No. 61/374,139 filed on Aug. 16, 2010, having the same title and which is incorporated in its entirety herein by reference.
This invention was made with government support from the U.S. Department of Energy under Cooperative Agreement No. DE-FC26-05NT42465 entitled “National Center for Hydrogen Technology” and the U.S. Army Construction Engineering Research Laboratory under Cooperative Agreement No. W9132T-08-2-0014 entitled “Production of JP-8-Based Hydrogen and Advanced Tactical Fuels for the U.S. Military.” The government has certain rights in the invention.
Number | Name | Date | Kind |
---|---|---|---|
1738620 | Umpleby | Dec 1929 | A |
2538219 | Welty, Jr. | Jan 1951 | A |
2600425 | Parry | Jun 1952 | A |
3746521 | Giddings | Jul 1973 | A |
3748254 | Gorin | Jul 1973 | A |
3920417 | Fernandes | Nov 1975 | A |
4069107 | Koppelman | Jan 1978 | A |
4239614 | Hutchings | Dec 1980 | A |
4272255 | Coates | Jun 1981 | A |
4309195 | Rotter | Jan 1982 | A |
4371378 | Brent | Feb 1983 | A |
4400181 | Snell et al. | Aug 1983 | A |
4479808 | Campbell | Oct 1984 | A |
4530702 | Fetters et al. | Jul 1985 | A |
4584947 | Chittick | Apr 1986 | A |
4707163 | Gudymov | Nov 1987 | A |
4826627 | Najjar | May 1989 | A |
4857203 | Pope et al. | Aug 1989 | A |
4857229 | Najjar et al. | Aug 1989 | A |
4859213 | Segerstrom | Aug 1989 | A |
4876031 | Najjar et al. | Oct 1989 | A |
4909958 | Najjar | Mar 1990 | A |
5026403 | Michel-Kim | Jun 1991 | A |
5562744 | R as anen | Oct 1996 | A |
5688296 | Andrus, Jr. | Nov 1997 | A |
6083862 | Wheelock | Jul 2000 | A |
6112677 | Kuntschar | Sep 2000 | A |
6680137 | Paisley | Jan 2004 | B2 |
6808543 | Paisley | Oct 2004 | B2 |
6960234 | Hassett | Nov 2005 | B2 |
20020069798 | Aguadas Ellis | Jun 2002 | A1 |
20020095866 | Hassett | Jul 2002 | A1 |
20020134019 | Paisley | Sep 2002 | A1 |
20040208810 | Simell et al. | Oct 2004 | A1 |
20040232046 | Tanaka | Nov 2004 | A1 |
20060265954 | Dogru et al. | Nov 2006 | A1 |
20070012229 | Rehmat | Jan 2007 | A1 |
20080073445 | Yu | Mar 2008 | A1 |
20080134581 | Van Dyk et al. | Jun 2008 | A1 |
20080202028 | Tsangaris et al. | Aug 2008 | A1 |
20090000194 | Fan et al. | Jan 2009 | A1 |
20090077891 | Duca et al. | Mar 2009 | A1 |
20090158658 | Stadler | Jun 2009 | A1 |
20090217574 | Coleman | Sep 2009 | A1 |
20100018115 | Wallace | Jan 2010 | A1 |
20100024300 | Chornet et al. | Feb 2010 | A1 |
20100037519 | Patil | Feb 2010 | A1 |
20100107493 | Weaver | May 2010 | A1 |
20100178217 | Alyaser | Jul 2010 | A1 |
Number | Date | Country |
---|---|---|
10030778 | Jan 2002 | DE |
0364074 | Apr 1990 | EP |
0386352 | Sep 1990 | EP |
1167492 | Jan 2002 | EP |
1312662 | May 2003 | EP |
302607 | Dec 1929 | GB |
01536654 | Dec 1978 | GB |
02144766 | Mar 1985 | GB |
2259521 | Mar 1993 | GB |
02290487 | Jan 1996 | GB |
2466260 | Jun 2010 | GB |
WO-1981001713 | Jun 1981 | WO |
WO-1989002909 | Apr 1989 | WO |
WO-1993022540 | Nov 1993 | WO |
WO-2000006672 | Feb 2000 | WO |
WO-00057105 | Sep 2000 | WO |
WO-00069994 | Nov 2000 | WO |
WO-00069995 | Nov 2000 | WO |
PCTCH0100001 | Jan 2001 | WO |
0151591 | Jul 2001 | WO |
200246331 | Jun 2002 | WO |
WO-020050214 | Jun 2002 | WO |
2005083041 | Sep 2005 | WO |
WO-06082543 | Aug 2006 | WO |
WO-07082089 | Jul 2007 | WO |
WO-08009433 | Jan 2008 | WO |
WO-08033812 | Mar 2008 | WO |
WO 2010022741 | Mar 2010 | WO |
Number | Date | Country | |
---|---|---|---|
20120036777 A1 | Feb 2012 | US |
Number | Date | Country | |
---|---|---|---|
61374139 | Aug 2010 | US |