1. Technical Field
The present invention relates generally to reactors, and more particularly to fabricating substrates that may be used in reactors.
2. Description of Related Art
Many reactions involving fluids (e.g., gases, liquids, and the like) use reactors. Many reactions are temperature dependent, and so a reactor (or zone within a reactor) may be required to have certain chemical, mechanical, thermal, and other properties at a temperature of interest to the reaction. Some reactions are performed at high temperatures (e.g., above 100 C, above 400 C, above 800 C, above 1100 C, or even above 1500 C), and so may require reactors having appropriate properties at the temperature of interest. Some reactions entail a heterogeneous reaction (e.g., involving a fluid and a surface).
Abatement of exhaust streams (e.g., from engines, turbines, power plants, refineries, chemical reactions, solar panel manufacturing, electronics fabrication, and the like) may include heterogeneous reactions. In some cases, the period of time during which a fluid interacts with a surface may affect the efficacy of a reaction. Certain reactions may benefit from increased contact times between a fluid and a substrate. Certain reactions may benefit from reduced contact times between a fluid and a substrate.
Some reactions proceed at practical rates at high temperatures. In some cases, an exhaust stream may provide heat that may heat a reactor (e.g., as in a catalytic converter on an automobile). Controlling both contact time (e.g., between a fluid and a reactor) and a temperature at which the reaction occurs may be challenging with typical reactor designs, particularly when heat transfer and mass transfer are not independently controlled.
Effective reaction (e.g., mitigation of a pollutant) may require a reactor design that maintains a desired temperature or range of temperatures over a certain volume or region having a certain surface area, notwithstanding that the primary source of heat to the reactor may be the exhaust stream. Such requirements may be challenging, particularly when mass transfer and/or reaction kinetics are at odds with heat transfer kinetics (e.g., from an exhaust stream to a reactor, or from the reactor to the environment).
The use of exhaust heat to maintain a reactor temperature may result in impaired performance under some conditions. For example, a catalytic converter may inefficiently decompose pollutants prior to having been heated to an appropriate temperature (e.g., when the vehicle is cold). A diesel particulate filter may require “regeneration” (e.g., the creation of a temperature and oxygen partial pressure sufficient to oxidized accumulated soot). Regeneration often requires heating the filtered soot to an oxidation temperature, which often relies on heat from the exhaust stream and/or heat from other sources. Regeneration may require electrical heating of a reactor. Some combinations of engines and duty cycles may result in contaminants (e.g., soot) reaching unacceptable levels before a mitigation system begins efficient operation (e.g., a soot filter may “fill up” before regeneration occurs.
Regeneration may require injection of a fuel and associated combustion heating beyond the motive heat associated with the working engine (e.g., direct injection of fuel into an exhaust stream). In some cases, the provision of regeneration heat (e.g., via electrical heating, post-injection, downstream injection, and the like) may decrease the overall efficiency of a system.
Some streams of fluids may be subject to a plurality of reactions and/or reactors. For example, a diesel exhaust mitigation system may include a diesel oxidation reactor (e.g., to oxidize CO and/or hydrocarbons), a particulate filter, and a reactor to remove NOx (oxides of Nitrogen). In some cases, these reactors are disposed in series, and so an exhaust system may include several components, each having an inlet and outlet, with the outlet of one component connected to the inlet of another component. Such systems may be complex and/or difficult to integrate.
In some cases, each component may require a separate mass and/or heat injection apparatus. For example, excess diesel fuel may be injected into an exhaust stream to create combustion at a diesel oxidation reactor in order to raise an inlet temperature of a particulate filter. A NOx reactor may require injection of a reductant, (e.g., urea, ammonia, Hydrogen, and/or other fuel) in order to facilitate a reaction at a certain temperature. A diesel particulate filter may benefit from NOx injection (e.g., to oxidize soot).
In some cases, latent heat and/or chemical species exiting a first reactor may not be efficiently utilized in a second “downstream” reactor, notwithstanding that the heat and/or species might be useful in the downstream reactor. In some cases, the heat and/or species exiting a first reactor must be controlled in such a way that performance of a downstream reactor is not inhibited. Improved reactor designs might provide for such control.
Many refractory substrates (e.g., catalytic converter, diesel particulate filter, and the like) are fabricated using extrusion. Such substrates often have long channels, with the “long” direction of the channels associated with the extrusion direction. The long direction may also be aligned with the flow of fluid through the substrate. As a result, reaction kinetics, heat transfer kinetics, fluid flow properties, and the like may be constrained by the method of fabrication of the substrate (e.g., extrusion). For example, a certain minimum residence time (associated with a reaction) may require a substrate having a minimum length, which may dictate an extruded substrate whose length is impractical for a given application.
For a typical filter (e.g., a diesel particulate filter, or DPF), filtration may preferentially begin at regions having higher fluid flow rates. In some cases, the deposition of particles may preferentially occur at the downstream end of a filter substrate, and so a particulate filter may “fill up” from the downstream end toward the upstream end.
A DPF may be “regenerated” by oxidizing filtered particles (e.g., filtered soot). Often, the downstream end of a DPF substrate may be cooler than the upstream end, and so regeneration of soot may require that the coolest part of the substrate reach regeneration temperatures. In certain applications, it may be advantageous to provide for preferential soot filtration at portions of the substrate that heat up faster than other portions.
Reactors and reactor substrates are described. Design guidelines are described. In some embodiments, a reactor design provides for improved control of heat transfer between a fluid and a reactor involved in a reaction with the fluid. Certain reactors may be used for filtration of particulates from a fluid stream. In some cases, preferential filtration may occur in regions of a reactor that are more amenable to regeneration. In some cases, soot may preferentially be filtered in regions of a reactor that reach regeneration temperatures sooner than other regions of the reactor.
Methods for forming reactors are described. Certain methods include depositing a layer of particulate material and bonding a portion of the layer using a bonding apparatus. Bonding may include incorporating a polymer into the layer, and in some cases, a laser may be used to fuse the portion. A layer may include a first material (e.g., a ceramic powder from which a reactor may be fabricated) and a second material (e.g., a binder to bind the powder). In certain embodiments, a fugitive phase is used, often in the range of 10-80% by weight, in order to enhance porosity. A fugitive phase may be present in an as-received ash source, such as a fly ash having substantial residual carbonaceous species. A fugitive phase may also be added separately. A layer may include a fugitive phase. A binder may behave as a fugitive phase. An activator may be deposited onto portions of the layer, which may activate bonding among the various particles exposed to the activator. A binder may include organic material (e.g., a polymer), which in some embodiments is oxidized to yield a porous body. A fugitive phase may be included. A fugitive phase may include a material whose incorporation into a body (e.g., bound to other materials forming the body) may be followed by a step that decomposes the fugitive phase, leaving pores associated with the shape, size, and/or distribution of the fugitive phase. A binder may include a fugitive phase.
Repeated deposition of layers with concomitant delineation of portions may be used to build up a substrate. Built up substrates may be sintered to remove a bonding polymer and form refractory bonds between particles. Substrates may be substantially comprised of ceramics (e.g., ash). Many suitable bodies are substantially porous (e.g., over 5%, 10%, 20%, 40%, 60%, 80%, or even over 90% porous). Substrates may have between 10 and 80% porosity.
An appropriately designed series of reactors may utilize the heat, mass flow, and chemical species from a first reactor to improve the performance of a second reactor connected to the first reactor.
A reactor may have an inlet and an outlet, and may include a substrate configured to react with (or provide for a reaction involving) a fluid passing from the inlet to the outlet. A line from the inlet to the outlet may describe a flow direction through the reactor. In some cases, the substrate includes a first end in fluid communication with the inlet and a second end in fluid communication with the outlet. The substrate may include one or more channels to treat a fluid (e.g., gas or liquid) passing from the inlet to the outlet. In some aspects the first channel is in fluid communication with the inlet and the outlet. The first channel may be shaped to cause a fluid flowing through the first channel to take a direction that deviates from the flow direction by at least 5 degrees, at least 10 degrees, at least 20 degrees, at least 30 degrees, or even at least 45 degrees. In some cases the deviation is less than 90 degrees.
Some channels are shaped and/or include features to induce secondary flows in the fluid flowing through the channel. A secondary flow (e.g., an eddy, a vortex, and the like) may increase a deposition of a species (e.g., soot) on a wall of the channel. A secondary flow may increase a residence time and/or contact time between the fluid and a wall of the channel. A secondary flow may provide for improved chemical reactions.
Some channels may be helical. In some cases, substrates may be comprised of helical channels, and an “interior” of the helix may be separated from the “exterior” of the helix by the substrate walls. In some cases, the interior may be in fluid communication with an inlet and an exterior may be in fluid communication with an outlet. The interior and exterior may be in fluid communication via one or more channels.
Certain embodiments include filters. In some cases, a first channel may be in fluid communication with an inlet to a reactor, and a second channel may be in fluid communication with an outlet of a reactor. The first and second channels may be separated by a porous wall, such that fluid passing from the first channel to the second channel may be filtered.
In certain embodiments, the first and second channels are helical. The first channel may be in fluid communication with an exterior of the helix, and the second channel may be in fluid communication with an interior of the helix (or vice versa).
Some reactors include a first substrate having a first channel configuration and a second substrate having a second channel configuration. The first and second substrates may be arranged in series (with respect to fluid flow). The first and second substrates may be arranged in parallel (with respect to fluid flow). In some cases, the first and second substrates are helical and coaxial. In some cases, the first and second substrates have different numbers of channels, channel shapes, flow patterns (e.g., flow through or wall flow), catalysts, channel cross sectional area to volume ratios, channel porosity, and other factors. First and second substrates may include different materials. A first substrate may be fabricated form SiC, and a second substrate may be fabricated from cordierite. A substrate may include ash, such as fly ash, and may include cenospheres.
Some substrates may be configured for filtration of particulate material (e.g., from diesel engines). Some designs provide for flow field instabilities that enhance the surface deposition of particulates on walls of various channels. Certain substrates provide for “virgin” substrates having a first portion of higher permeability than a second portion. Some substrates provide for a preferential flow and/or filtration of particles in a region that heats up (e.g., from exhaust gas heat) more quickly than a second region.
Some substrates include channels having “channel plugs” that are disposed within the substrate. In some cases, channel walls are configured to perform as channel plugs, which may increase a surface area of the “plugs” in some embodiments.
A substrate for use in a reactor having an inlet and an outlet, the substrate may include a plurality of tubular first channels in fluid communication with the inlet, the tubular first channels including channel walls, at least a portion of the channel walls having a porosity greater than 20%; the plurality of tubular first channels connected to each other by their channel walls. The substrate may include a plurality of second channels in fluid communication with the outlet, the plurality of second channels having shapes that correspond to the interstitial volumes between the plurality of tubular first channels. The plurality of tubular first channels may be square packed, trigonally packed, hexagonally packed, and/or randomly packed. In some cases, a random packing may provide for a diversity cross sectional areas in the plurality of second channels.
Various aspects provide for reactors and the fabrication of reactors. Some reactors include surfaces that provide for heterogeneous reactions involving a fluid (and/or components thereof). A fluid may be a gas and/or a liquid. A contaminant in the fluid (e.g., a dissolved or suspended substance) may react in a reaction. Some reactors provide for independent control of heat transfer (between the fluid, the reactor, and the environment) with respect to mass transfer (e.g., fluid flow through the reactor).
The design of a reactor may incorporate a combination of properties describing a fluid to be reacted. For example, a reactor comprising a catalytic converter may be designed according to an engine type (2 stroke, 4 stroke, Atkinson cycle, Otto cycle, and the like), an amount of electrical hybridization (non-hybrid, mild hybrid, full hybrid), an expected duty cycle (garbage truck, backup generator, string trimmer, tug boat, locomotive, and the like), a fuel source (bunker fuel, ULSD, gasoline, E85, biodiesel, premixed oil/gas solutions), and the like. Some reactors may be “disposable.”
A substrate is typically contained within a package, such as package 120. A package may prevent uncontrolled mass transfer with the environment. Package 120 may be designed to improve heat flow into or out of the reactor (e.g., insulated at certain portions and/or heat fins at certain portions).
In many reactors, a fluid enters the inlet at a certain temperature with a certain composition and exits the reactor at another temperature and another composition. Chemical reactions inside the reactor may be influenced (or even controlled) by heat transfer from the fluid to the substrate (and by extension between reactor 100 and the environment).
Surfaces of a substrate may be coated with a catalyst to modify a reaction. A fluid may include a catalyst (e.g., dispersed in the fluid, such as a fuel-borne catalyst). A catalyst may be injected into a reactor (e.g., upstream of the substrate). In some embodiments, a catalyst may be injected between the upstream and downstream regions of a substrate.
Certain embodiments include channels that may be characterized as tubular. In some cases, tubes may be square packed (e.g., a tube contacting four other tubes), hexagonally close packed (e.g., a tube touching six other tubes), trigonally packed (e.g., a tube touching three other tubes). In some examples, a tube touches five other tubes. Packing of tubes may be modified to control (inter alia) the relative cross sectional area of upstream channels to downstream channels.
Eddies 360 may enhance a deposition of entrained particulates (e.g., in a fluid in an upstream channel), as illustrated by deposit 370. In some embodiments, a flow-through filter may trap substantial quantities of entrained particles by providing a large number of flow modifiers in upstream channels. Some embodiments may result in improved resistance to clogging by deposited particles. Flow modifiers may be used to (e.g., in a downstream channel) to slow the flow of fluid through the channel, which may result in increased transfer of heat from the fluid to the substrate prior to exiting the substrate. Certain embodiments include a helical flow modifier, which may increase the transfer of heat from a fluid to the substrate.
Various embodiments include channels designed to induce secondary flows in a fluid (e.g., in addition to a primary flow describing flow of the fluid through or past a substrate). Secondary flows may be associated with instabilities in the flow field describing the fluid, and may result from features that induce a change in the flow path of the fluid. Curves and/or curvature in a channel may cause such instabilities. Flow modifiers may cause such instabilities. In some cases, a feature and/or shape of a substrate may result in an induced instability and/or be associated with a vortex or vortices. Certain substrates may induce Taylor vortex flow, Taylor-Couette flow, wavy vortex flow, spiral vortex flow, and/or other instabilities in a fluid. Some substrates may induce turbulent flow. Some embodiments includes channels having a changing cross sectional area with position in a fluid flow path (e.g., a decreasing cross sectional area, an increasing cross sectional area, a “neck” in the path, and the like).
In some embodiments, channel walls substantially form the upstream and/or downstream plugs. In such cases, the surface area of the “plugs” may approach the surface area of the channels. For example, the circular cross sections at the upstream end of upstream channels 420 may be “flared” at the upstream end to form hexagonal cross sections, which may increase the total cross sectional area of upstream channels exposed to inlet 410. A transition from upstream to downstream need not be monotonic (e.g., conical as shown in
Channels may be separated by channel walls 440. In some embodiments, a fluid enters upstream channels 410, passes through channel walls 440 into downstream channels 430. Substrate 400 may be implemented as a filter.
Substrate 400 may be characterized by a length 470. In some embodiments, the cross sectional area of upstream and/or downstream channels may vary as a function of the length. In the example shown in
Substrate 600 also illustrates a transition region in cross sectional area of a channel. In this example, a transition region 680 in downstream channels 630 is illustrated. Downstream channels 630 may include a first cross section 634 (in this case, approximately defined by the interstitial area between upstream channels 620). Downstream channels 630 may also include a second cross section 636 (in this case, larger cross sections toward the downstream end of substrate 600. Transition region 680 may generally describe a transition between first cross sections 432 and second cross sections 434.
In some embodiments, transition region 680 may be located approximately midway between upstream and downstream faces of substrate 600. In some embodiments, transition region 680 may be located within 10% of length 670 of either an upstream or downstream face of substrate 600. In some embodiments, transition region 680 may be located approximately 10%, 20%, 30%, 40%, 50%, 70%, 80%, or 90% along length 670.
Downstream plug 760 may form an “end” of upstream channel 720. For convenience, downstream plug 760 is referred to as “downstream” (e.g., with respect to fluid flow), although downstream plug 760 may be disposed at various points in reactor 700 (e.g., even at the upstream face of the reactor, as shown in
In some embodiments, porosity, mean pore size, pore size distribution, channel cross section, wall thickness, tortuosity, and other factors may vary as a function of length along a channel. For example, a region 770 of wall 730 (close to inlet 722) may have a first pore size distribution, a region 780 of wall 730 (close to downstream plug 760) may have a second pore size distribution, and/or a region 790 (close to outlet 742) may have a third pore size distribution. Pore connectivity and/or pore shape may be isotropic or anisotropic. In some aspects, a pore connectivity may be designed that optimizes both fluid interaction and mechanical properties. Some porosity may be anisotropic with respect to (e.g.,) various body dimensions. A pore size distribution may take a variety of forms, including Gaussian, normal, lognormal, multimodal, bimodal, trimodal, skewed, Weibull, or any other desired distribution. Porosity may also be characterized by macroscopic factors (e.g., % porosity, surface area, permeability and the like). Various applications may require different combinations of mean pore diameter and percentage open porosity.
In some cases, these factors may be used to control permeability through a wall as a function of position in the reactor. In some cases, control of permeability may include control of the time dependence of the permeability (e.g., as soot loading in the channel increases). A region 780 may have a higher permeability than a region 790. A region 770 may have a higher permeability than a region 790.
In some filtration applications (e.g., as a particulate filter) wall 730 may be fabricated such that particulate loading begins close to downstream plug 760. With downstream plug 760 designed to be close to inlet 722 (e.g., proximate to the upstream side of reactor 700), soot loading may occur preferentially in regions of reactor 700 that reach oxidation temperatures quickly (as compared to regions proximate to outlet 742).
Certain components (e.g., substrates) may be fabricated from ceramics, such as SiC, Si3N4, cordierite, mullite, Al-titanates, and composites thereof. Substrates may be fabricated from fly ash. Precursor materials may include MgO, SiO2, colloidal SiO2, TiO2, FeO, Talc, kaolin, boehmite, various Al2O3 species (e.g, γ-Al2O3, α-Al2O3), gypsum, phosphorous-containing compounds, SiC, Al, Co, Fe, Ni, Ba, Pb, lanthanides, sulfides, zeolites, rare earth compounds and the like.
Substrates may have porosity ranging from 10-90%, including between 20 and 70%. Substrates may have a surface area greater than 10 square inches/gram, and may be greater than 100 square inches/gram, or even greater than 1000 square inches/gram. Some substrates (e.g., for filtration) may have a pore size distribution characterized by a median pore size and/or a mean pore size between 1 and 100 microns, including between 4 and 80 microns, and/or between 10 and 50 microns. Some walls (e.g., between channels) may have a permeability greater than 0.5E-12/m^2, or even greater than 1E-12/m^2, including greater than 10E-12/m^2.
In some embodiments, inlet surface 810 may be disposed facing in incoming fluid stream, outlet surface 820 may be disposed toward an outlet, and a fluid may be treated by passing through walls 840. Channel exits 850 may facilitate a passage of treated fluid from interior regions of substrate 800 to an outlet.
In some aspects, portions of substrate 800 may be shaped to alter fluid flow. For example, some upstream faces 860 of inlet surface 810. Some upstream surfaces 870 of inlet surface 810 may be concave. Downstream or side surfaces may also be shaped to modify fluid flow, and flow modifiers may be included. Substrate 800 may include a channel plug 862, which may be located proximate to an “upstream” face associated with fluid flow. A channel plug may be porous, and may have a similar or different porosity than other portions of the channel. A channel may redirect fluid from from a direction toward the downstream face to a direction toward the upstream face, and/or a direction toward the upstream face to a direction toward the downstream face.
A channel width 1012 and height 1014 may be chosen in combination with pitch 1030 to control a flow rate through the channel. For example, a smaller pitch may be used to reduce flow rate; a larger pitch may increase flow rate. A ratio of channel volume to channel surface area may be controlled by the ratio of height 1014 to width 1012. In some embodiments, height 1014 and width 1012 are approximately equal. In some embodiments, width 1012 is larger than height 1014 (e.g., 2×, 5×, 10×, 100×, or even 1000×larger). In some embodiments, height 1014 is larger than width 1012. In some cases (e.g., for small pitches 1030), the length of channel 1010 may be much greater than length 1040 of a reactor, which may provide for increased contact time between a fluid being treated (passing from inlet opening 1050 to outlet opening 1060). An increased residence time may result in a greater amount of heat being transferred from a fluid to the reactor. In some cases, a catalyst 1012 may be disposed on a surface of channel 1010. In some embodiments, a first wall thickness 1080 between adjacent channels 1010 is different than a separate wall thickness 1082 associated with a wall between channel 1010 and the “outer volume” of a reactor containing substrate 1000. In some cases, wall thickness 1082 is substantially thicker (e.g., twice, five times, or even ten times thicker) than wall thickness 1080.
In some embodiments, the expected fluid flow properties may be used to calculate dimensions of various channels, and in some cases an “inner” channel having a tighter curvature may have a larger cross sectional area than an “outer” channel having a more gentle curvature. In some embodiments, an “outer” channel may have a pitch, curvature, and/or dimensions that result in preferential fluid flow through the outer channel vs. an “inner” channel. In some embodiments, an “inner” channel may have a pitch, curvature, and/or dimension that results in preferential fluid flow through the “inner” channel vs. an “outer” channel. “Inner” and “outer” channels may have different pitches (e.g., not be coplanar with respect to channel 1310 as shown in
In some cases, a reactor and/or substrate design may include an expected deposition of particles (e.g., clogging), and an expected flow pattern may evolve as clogging increases. For example, substrate properties (e.g., channel shapes, sizes, and number) that result in an “outside-in” bias to a flow pattern. An unclogged substrate may cause fluid to preferentially flow through outer channels. As outer channels become clogged, fluid flow through inner channels may increase. In some cases, an unclogged substrate may cause fluid to preferentially flow through inner channels. As the inner channels become clogged, fluid flow through the outer channels may increase.
Some embodiments include a first channel and second channel separated by a porous wall. A fluid may be filtered upon passing from the first to second channels via the porous wall. The second channel may be configured to treat the filtered fluid. In some cases, a first channel mitigates a first contaminant (e.g., hydrocarbons), and a second channel mitigates another contaminant. In some cases, a first channel mitigates NOx and a second channel mitigates particulate matter.
In an exemplary embodiment, a helical reactor incorporates a first channel as in channel 1404 adjacent to a second channel as in channel 1406. Channels 1404 and 1406 may be separated by a porous wall. Fluid may pass through inlet 1414 in fluid communication with an inlet of the reactor, through the walls into adjacent channels 1406, then exit the channels 1406 via outlets 1416 to the interior of the helix. In such a configuration, “filtration” may occur primarily in a direction normal to the page of
Two or more substrates may be connected to form a third substrate. Two or more channels may be connected to form a combination of channels. In some cases, reactors may be “integrated” by providing a first channel that performs a first reaction and a second channel that performs a second reaction. Heat and mass transfer calculations may be used to determine a combination of geometrical and materials factors that may result in an integrated reactor using available heat and/or chemicals from a first reactor to improve a reaction in a second reactor.
In some cases, one of the two substrates may be in fluid communication with an inlet to a reactor containing substrate 2200, and another substrate may be in fluid communication with an outlet of the reactor. An outlet to one of the substrates may be in fluid communication with an inlet of the other substrate.
Many reactors transfer heat to and from the environment. In some cases, heat transfer may proceed “radially” with respect to a helical substrate (e.g., a hot substrate loses heat to the environment in a radially “outward” direction. Some applications may benefit from “nesting” a first substrate within a second substrate. In some cases, fluid first flow through an outer first substrate, then flows through an inner second substrate. In some cases, fluid first flows through an inner first substrate, then flows through an outer second substrate. Fluid may flow through both substrates simultaneously. A first substrate may be configured to provide treatment under a first condition (e.g., a cold engine and/or stop/start operation) and a second substrate may be configured to provide treatment under a second condition (e.g., a hot engine and/or sustained, steady state operation).
Mixtures of particle size distributions may be used. In some embodiments, one or more particulate materials having broad particle size distributions is identified, the material is sieved to create sequential “cuts” of various particle size ranges, and one or more cuts is selected. Particles may have a relatively narrow particle size distribution, a wide particle size distribution, a bimodal or multimodal particle size distribution or other distribution as desired. Some properties may be enhanced by using a multimodal particle size distribution. In certain cases, a mixture of between 30-90% of a large particle size cut (e.g., particles greater than 10, 20, 30, 40, 50 or more microns) may be combined with a complementary amount of a small particle size cut (e.g., below 10, 5, 3, 1, or 0.1 microns). In certain embodiments, a bimodal particle size distribution is used, with first and second distributions mixed in approximately equal amounts, and the second distribution having a mean particle size that is ˜5-25% of the mean particle size of the first. Certain compositions may first form a liquid phase during firing that first enhances bonding, then reacts to form a solid phase (e.g., as in reactive sintering).
A separate binder may also be incorporated into the precursor material, and may be dispensed by carrier 1830 (e.g., as a mixture of binder and precursor material powders). A binder may also be dispensed as a separate layer (e.g., sequential layers of binder and precursor material). A binder may include polyethylene, a thermosetting resin, polycarbonate, a sugar, a starch, and the like. A binder may include an organic powder that reacts with an activator (e.g., a solvent) to cause the binder to glue various other particles (e.g., ceramic particles) to each other. For example, a substrate may be fabricated from cordierite powder, which may be dispensed as a mixture with powdered sugar. An activator (e.g., water) may be preferentially deposited on portions of a layer of the mixture, bonding the cordierite powder in the activated portion. A cementitious precursor material 1840 (or a pozzolanic material and a complementary material such as CaO) may be activated by an aqueous activator.
A bonder 1840 (e.g., a laser for thermal bonding, an inkjet to apply a binder or activator, and the like) may be configured to bond at least a portion of the dispensed layer. Bonder 1840 may activate bonding among particles of precursor material 1840 and/or among a binder and precursor material 1840. Typically, bonding may create a solidified portion of precursor material 1840, shown as structure 1850. After bonding, bottom 1820 may descend a small amount (e.g., microns to millimeters), carrier 1830 may dispense another layer of precursor material 1840 (with or in addition to additional binder), and bonder 1840 may bond an additional portion of the new precursor material 1840, adding an additional layer to structure 1850. In some embodiments, structure 1850 may include a substrate, channel, and the like. In some cases, a binder may be omitted. Companies such as 3D Systems (Rock Hill, S.C.), The Ex-One Company (Irwin, Pa.) and Z-Corporation (Burlington, Mass.) may provide some equipment for fabricating reactors. Various methods may be used to fabricate refractory (e.g., metallic, ceramic, and the like) having porosity greater than 10%, greater than 20%, greater than 30%, greater than 40%, or even greater than 50%.
Printing methods (e.g., inkjet printing) may also be used to form reactors. For example, a bonder 1840 may provide for spatially controlled deposition of a precursor material (e.g., as in an inkjet printing head). Tape casting may be used for some embodiments.
Fabrication of substrate 1900 may include changing the precursor material delivered by carrier 1830 in system 1800. For example, a first part of substrate 1900 may be fabricating by delivering (e.g., layering) a first material 1910, a second part of substrate 1900 may be fabricated by delivering (e.g., layering) a second material 1920, and a third part of substrate 1900 may be fabricated by delivering (e.g., layering) a third material 1930. Changing precursor material as a function of layer may provide for functionally graded properties in a “z” or “vertical” direction of a reactor (with respect to fabrication according to system 1800). Different precursor materials may be used to make a stratified body, (e.g., with layers of different particles disposed at different points). A precursor material may include anisotropic particles (e.g., whiskers, platelets).
Some bodies may be fired. Firing may be used to remove a fugitive phase (e.g., via combustion of a carbonaceous fugitive phase). Firing may also be used to aid the formation of interparticle bonds (e.g., necks). Firing may also be used to change the composition, crystal structure, particle size, grain size, and other aspects of a body. Select embodiments include selecting a first phase for forming a body, reacting the first phase to form a second phase during a forming operation, and in some cases, forming a third phase during a firing operation.
Firing times and temperature may generally depend upon a desired application and body properties directed thereto. Generally, applications requiring more refractory bodies may require equivalently higher firing temperatures. In some aspects, bodies are fired at temperatures between 400 and 800 Celsius. Bodies may be fired at temperatures between 800 and 1200 degrees Celsius. Some bodies may be fired at temperatures between 1200 and 1800 degrees. Some bodies including cordierite may be fired at temperatures between 1000 and 1600 degrees. Some bodies including mullite may be fired at temperatures between 1000 and 1950 degrees. Bodies requiring low temperature firing may be enhanced by using ashes containing network modifiers such as K2O and Na2O, or by adding these components. Bodies for use at temperatures above 500 Celsius may perform better by choosing an ash source having low (preferably negligible) amounts of less refractory materials such as K2O and Na2O. Certain compositions may form a liquid phase that first enhances bonding, then reacts to form a solid phase (e.g., as in reactive sintering).
Certain aspects include firing in a coal fired, gas fired, microwave enhanced, and/or electric furnace. In some cases, firing includes controlled atmospheres, which may include oxidizing, reducing, forming gas, Nitrogen, and other atmospheres. Firing may be done in air. Some bodies do not require firing. Firing atmospheres may include the addition of a gaseous component to prevent an undesired evolution of a substance during firing (e.g., an overpressure of a gas).
In some embodiments, a body is formed having a first pore size distribution, the body is treated with a fluid containing particles that are substantially filtered by the body, the fluid is removed (leaving the particles), and the body and particles are processed (e.g., fired) to create a body having a second pore size distribution. An exemplary fluid may be air, and exemplary particles may be fine particles yielding a composition similar to (or complementary to) a composition of the body.
The above description is illustrative and not restrictive. Many variations of the invention will become apparent to those of skill in the art upon review of this disclosure. The scope of the invention should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims along with their full scope of equivalents.
This application is a division and claims the priority benefit of U.S. patent application Ser. No. 13/593,564, now U.S. Pat. No. 8,679,418, filed Aug. 24, 2012, which is a division and claims the priority benefit of U.S. patent application Ser. No. 12/756,987, now U.S. Pat. No. 8,277,743, filed Apr. 8, 2010, which claims the priority benefit of U.S. provisional patent application No. 61/167,857, filed Apr. 8, 2009, the disclosures of which are incorporated herein by reference. This description is related to U.S. patent application Ser. No. 12/183,917, now U.S. Pat. No. 7,981,375, filed Jul. 31, 2008, the disclosure of which is incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
293745 | Hyatt | Feb 1884 | A |
1852489 | Sullivan | Apr 1932 | A |
2449822 | Schibbye | Sep 1948 | A |
2544752 | Gelbman | Mar 1951 | A |
2892240 | Frankenhoff | Jun 1959 | A |
2926137 | Calvert | Feb 1960 | A |
2946112 | Tucker, Jr. | Jul 1960 | A |
3343680 | Rice et al. | Sep 1967 | A |
3505008 | Frevel et al. | Apr 1970 | A |
3574530 | Suriani et al. | Apr 1971 | A |
3704786 | Lerner | Dec 1972 | A |
3739553 | Aine | Jun 1973 | A |
3824196 | Benbow et al. | Jul 1974 | A |
3885977 | Lachman | May 1975 | A |
3940301 | Straw | Feb 1976 | A |
3942990 | Engstrom et al. | Mar 1976 | A |
3953562 | Hait | Apr 1976 | A |
3953703 | Hurwitt | Apr 1976 | A |
3954672 | Somers et al. | May 1976 | A |
3957694 | Bolon | May 1976 | A |
3975201 | Greenstein | Aug 1976 | A |
3991149 | Hurwitt | Nov 1976 | A |
4006533 | Squires | Feb 1977 | A |
4025462 | Cleveland | May 1977 | A |
4041591 | Noll et al. | Aug 1977 | A |
4041592 | Kelm | Aug 1977 | A |
4069063 | Ball | Jan 1978 | A |
4071369 | Kurz | Jan 1978 | A |
4073729 | Kraemer et al. | Feb 1978 | A |
4080414 | Anderson et al. | Mar 1978 | A |
4107013 | McGinniss et al. | Aug 1978 | A |
4110187 | Sloan | Aug 1978 | A |
4120735 | Smith | Oct 1978 | A |
4124365 | Williams | Nov 1978 | A |
4142864 | Rosynsky | Mar 1979 | A |
4166037 | Montagnon | Aug 1979 | A |
4190533 | Hirs | Feb 1980 | A |
4191546 | Kroyer | Mar 1980 | A |
4197205 | Hirs | Apr 1980 | A |
4225443 | Harris | Sep 1980 | A |
4253992 | Soejima et al. | Mar 1981 | A |
4254616 | Siminski et al. | Mar 1981 | A |
4255166 | Gernand et al. | Mar 1981 | A |
4264346 | Mann | Apr 1981 | A |
4276062 | Lyon | Jun 1981 | A |
4276071 | Outland | Jun 1981 | A |
4293514 | Wada | Oct 1981 | A |
4329162 | Pitcher, Jr. | May 1982 | A |
4353854 | Oyamada et al. | Oct 1982 | A |
4379039 | Fujimoto | Apr 1983 | A |
4415344 | Frost | Nov 1983 | A |
4416675 | Montierth | Nov 1983 | A |
4430108 | Hojaji et al. | Feb 1984 | A |
4436682 | Knopp | Mar 1984 | A |
4440867 | Sabherwal | Apr 1984 | A |
4452635 | Noshi et al. | Jun 1984 | A |
4483944 | Day | Nov 1984 | A |
4587068 | Borase et al. | May 1986 | A |
4601332 | Oda | Jul 1986 | A |
4613374 | Smith | Sep 1986 | A |
4626359 | Bennett et al. | Dec 1986 | A |
4629483 | Stanton | Dec 1986 | A |
4637995 | DeAngelis | Jan 1987 | A |
4645605 | Durham | Feb 1987 | A |
4652411 | Swarr et al. | Mar 1987 | A |
4681788 | Barito | Jul 1987 | A |
4743382 | Williamson | May 1988 | A |
4747945 | Kreusch | May 1988 | A |
4765545 | Van Kruining | Aug 1988 | A |
4777153 | Sonuparlak | Oct 1988 | A |
4786342 | Zellner et al. | Nov 1988 | A |
4804521 | Rochelle | Feb 1989 | A |
4863538 | Deckard | Sep 1989 | A |
4871495 | Helferich | Oct 1989 | A |
4877506 | Fee et al. | Oct 1989 | A |
4883497 | Claar et al. | Nov 1989 | A |
4888054 | Pond | Dec 1989 | A |
4898105 | Rappoldt | Feb 1990 | A |
4898631 | Collins, Jr. | Feb 1990 | A |
4944817 | Bourell et al. | Jul 1990 | A |
4964888 | Miller | Oct 1990 | A |
4968460 | Thompson et al. | Nov 1990 | A |
4971601 | Najjar | Nov 1990 | A |
4973459 | Lippert et al. | Nov 1990 | A |
4976760 | Helferich | Dec 1990 | A |
5002710 | Shanefield | Mar 1991 | A |
5071449 | Sircar | Dec 1991 | A |
5078795 | Conner et al. | Jan 1992 | A |
5086093 | Miller | Feb 1992 | A |
5096464 | Yamamoto | Mar 1992 | A |
5100633 | Morrison | Mar 1992 | A |
5108614 | Ross et al. | Apr 1992 | A |
5145826 | Hirschberg et al. | Sep 1992 | A |
5203936 | Dolhert | Apr 1993 | A |
5204055 | Sachs et al. | Apr 1993 | A |
5215724 | Haerle | Jun 1993 | A |
5221484 | Goldsmith | Jun 1993 | A |
5229078 | Haerle | Jul 1993 | A |
5232955 | Csabai et al. | Aug 1993 | A |
5238057 | Schelter | Aug 1993 | A |
5240485 | Haerle | Aug 1993 | A |
5244726 | Laney et al. | Sep 1993 | A |
5256609 | Dolhert | Oct 1993 | A |
5266279 | Haerle | Nov 1993 | A |
5275771 | Bush | Jan 1994 | A |
5279994 | Kerkar | Jan 1994 | A |
5284695 | Barlow | Feb 1994 | A |
5292436 | Mathews | Mar 1994 | A |
5306646 | Lauf | Apr 1994 | A |
5308457 | Dalla Betta et al. | May 1994 | A |
5322562 | Ellenberger et al. | Jun 1994 | A |
5335492 | Zirkel | Aug 1994 | A |
5345761 | King et al. | Sep 1994 | A |
5364573 | Noky | Nov 1994 | A |
5401481 | Rochelle et al. | Mar 1995 | A |
5401695 | Wu | Mar 1995 | A |
5405571 | Truckner | Apr 1995 | A |
5409870 | Locker | Apr 1995 | A |
5425236 | Haerle | Jun 1995 | A |
5427721 | Brezny | Jun 1995 | A |
5429779 | Locker | Jul 1995 | A |
5433904 | Noky | Jul 1995 | A |
5456965 | Machida | Oct 1995 | A |
5473008 | Hessel et al. | Dec 1995 | A |
5476375 | Khinkis | Dec 1995 | A |
5497620 | Stobbe | Mar 1996 | A |
5498288 | Noky | Mar 1996 | A |
5519087 | Tang | May 1996 | A |
5525665 | Moeggenborg et al. | Jun 1996 | A |
5547640 | Kim | Aug 1996 | A |
5551971 | Chadderton et al. | Sep 1996 | A |
5626763 | Mathews | May 1997 | A |
5639402 | Barlow et al. | Jun 1997 | A |
5645730 | Malachosky et al. | Jul 1997 | A |
5658372 | Gadkaree | Aug 1997 | A |
5686039 | Merry | Nov 1997 | A |
5705444 | Tompkins et al. | Jan 1998 | A |
5707574 | Domesle et al. | Jan 1998 | A |
5711833 | Apte et al. | Jan 1998 | A |
5714228 | Beckmeyer | Feb 1998 | A |
5728198 | Acharya et al. | Mar 1998 | A |
5731562 | Beckmeyer | Mar 1998 | A |
5733352 | Ogawa | Mar 1998 | A |
5750026 | Gadkaree et al. | May 1998 | A |
5753274 | Wilkening | May 1998 | A |
5766528 | Su | Jun 1998 | A |
5901683 | Patel | May 1999 | A |
5904892 | Holmes et al. | May 1999 | A |
5965257 | Ahluwalia | Oct 1999 | A |
5983488 | Erickson | Nov 1999 | A |
5997794 | Huang et al. | Dec 1999 | A |
6136088 | Farrington | Oct 2000 | A |
6196344 | Tamor et al. | Mar 2001 | B1 |
6200379 | Strabala | Mar 2001 | B1 |
6238618 | Brundage et al. | May 2001 | B1 |
6258334 | Gadkaree et al. | Jul 2001 | B1 |
6290847 | Cutler | Sep 2001 | B1 |
6296794 | Day et al. | Oct 2001 | B1 |
6322605 | He et al. | Nov 2001 | B1 |
6328779 | He et al. | Dec 2001 | B1 |
6368102 | Ibrahim | Apr 2002 | B1 |
6375451 | Robinson et al. | Apr 2002 | B1 |
6405875 | Cutler | Jun 2002 | B1 |
6409817 | Stephens | Jun 2002 | B1 |
6421599 | Lippa et al. | Jul 2002 | B1 |
6440198 | Yang | Aug 2002 | B1 |
6454941 | Cutler et al. | Sep 2002 | B1 |
6461632 | Gogolewski | Oct 2002 | B1 |
6464744 | Cutler | Oct 2002 | B2 |
6468325 | Cutler | Oct 2002 | B1 |
6492119 | Ogawa | Dec 2002 | B1 |
6612835 | Ibrahim | Sep 2003 | B2 |
6613299 | Dang et al. | Sep 2003 | B2 |
6673300 | Allen et al. | Jan 2004 | B2 |
6695967 | Bishop et al. | Feb 2004 | B2 |
6696132 | Beall | Feb 2004 | B2 |
6743513 | Mechlosky et al. | Jun 2004 | B2 |
6755016 | Dittler et al. | Jun 2004 | B2 |
6770111 | Morena et al. | Aug 2004 | B2 |
6827754 | Suwabe et al. | Dec 2004 | B2 |
6835224 | Cheng | Dec 2004 | B2 |
6843822 | Beall | Jan 2005 | B2 |
6849181 | Ogunwumi | Feb 2005 | B2 |
6881703 | Cutler et al. | Apr 2005 | B2 |
6883321 | Fornof | Apr 2005 | B2 |
6887291 | Alford et al. | May 2005 | B2 |
6890616 | Suwabe et al. | May 2005 | B2 |
6923941 | Huthwohl et al. | Aug 2005 | B2 |
6942767 | Fazzina et al. | Sep 2005 | B1 |
6946013 | Alward | Sep 2005 | B2 |
6991668 | Towsley | Jan 2006 | B2 |
7008461 | Kuki | Mar 2006 | B2 |
7011803 | Ichikawa et al. | Mar 2006 | B2 |
7087109 | Bredt et al. | Aug 2006 | B2 |
7110904 | Lippa et al. | Sep 2006 | B2 |
7112233 | Ohno et al. | Sep 2006 | B2 |
7279022 | Johnson | Oct 2007 | B2 |
7291197 | Costura et al. | Nov 2007 | B2 |
7328805 | Price et al. | Feb 2008 | B2 |
7340887 | Ante et al. | Mar 2008 | B2 |
7514010 | Salmon | Apr 2009 | B2 |
7585352 | Dunn | Sep 2009 | B2 |
7655088 | Bethani | Feb 2010 | B2 |
7674423 | Sano | Mar 2010 | B2 |
7691319 | Inoue et al. | Apr 2010 | B2 |
7695559 | Chartier et al. | Apr 2010 | B1 |
7736430 | Barron et al. | Jun 2010 | B2 |
7749476 | Constantz et al. | Jul 2010 | B2 |
7754169 | Constantz et al. | Jul 2010 | B2 |
8007573 | Bansal et al. | Aug 2011 | B2 |
20020003112 | Golden | Jan 2002 | A1 |
20020014051 | Fraval | Feb 2002 | A1 |
20050059757 | Bredt | Mar 2005 | A1 |
20050109023 | Kudo | May 2005 | A1 |
20050110177 | Schulman | May 2005 | A1 |
20050161849 | Ohno | Jul 2005 | A1 |
20050232827 | Merry | Oct 2005 | A1 |
20050265915 | Tonkovich et al. | Dec 2005 | A1 |
20060107658 | Hiranuma et al. | May 2006 | A1 |
20060162619 | Bethani | Jul 2006 | A1 |
20060162929 | Urbanek | Jul 2006 | A1 |
20060210765 | Ohno | Sep 2006 | A1 |
20060228521 | Ohno | Oct 2006 | A1 |
20060251909 | Beall et al. | Nov 2006 | A1 |
20060272319 | Dettling et al. | Dec 2006 | A1 |
20060287197 | Maslanka | Dec 2006 | A1 |
20070006561 | Brady et al. | Jan 2007 | A1 |
20070032370 | Weisensel et al. | Feb 2007 | A1 |
20070041880 | Reinsch et al. | Feb 2007 | A1 |
20070179056 | Baek et al. | Aug 2007 | A1 |
20070224565 | Briselden | Sep 2007 | A1 |
20070238056 | Baumann | Oct 2007 | A1 |
20070261378 | Miao et al. | Nov 2007 | A1 |
20070263477 | Sudarsan et al. | Nov 2007 | A1 |
20070263485 | Yang et al. | Nov 2007 | A1 |
20080014405 | Sakamoto | Jan 2008 | A1 |
20080017572 | Kudo | Jan 2008 | A1 |
20080017573 | Pyzik et al. | Jan 2008 | A1 |
20080044319 | Takahashi et al. | Feb 2008 | A1 |
20080072551 | Zuberi | Mar 2008 | A1 |
20080128331 | Lean et al. | Jun 2008 | A1 |
20080226346 | Hull et al. | Sep 2008 | A1 |
20080271422 | Zawisza | Nov 2008 | A1 |
20080314242 | Cochran et al. | Dec 2008 | A1 |
20090044515 | Lu et al. | Feb 2009 | A1 |
20100083834 | Varadaraj | Apr 2010 | A1 |
20100101464 | Leach | Apr 2010 | A1 |
20100143215 | Caze | Jun 2010 | A1 |
20100183490 | Hoke et al. | Jul 2010 | A1 |
20100251937 | Murray et al. | Oct 2010 | A1 |
20110100910 | Johansen et al. | May 2011 | A1 |
20120082601 | Sutherland | Apr 2012 | A1 |
20120148457 | Sutherland | Jun 2012 | A1 |
Number | Date | Country |
---|---|---|
0337047 | Oct 1989 | EP |
1600202 | Nov 2005 | EP |
19870363083 | Feb 1987 | JP |
1997025155 | Sep 1997 | JP |
1988143913 | Jun 1998 | JP |
11029346 | Feb 1999 | JP |
2002248498 | Sep 2002 | JP |
2005060159 | Mar 2005 | JP |
2005-034797 | Oct 2005 | JP |
20060004920 | Jan 2006 | JP |
2003002221 | Jan 2003 | KR |
Entry |
---|
Office Action issued May 22, 2014 in U.S. Appl. No. 13/171,489. |
Mechanical translation of Final Decision received Jun. 2014 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793. |
Final Decision received Jul. 2014 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793. |
Recection Decision received Jun. 2014, issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Translation of Recection Decision received Jun. 2014, issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Response to Rejection Decision issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Response to Communication pursuant to Article 94(3) EPC,in associated European Patent Application No. 08 796 966, which is the National Stage of PCT/US2008/071793. |
Article 94(3) Communcation from European Patent Office in European Patent Application No. 08 796 966.3. |
Office Action issued Dec. 15, 2014 in U.S. Appl. No. 13/171,489. |
U.S. Appl. No. 12/699,736, Ramberg, Porous Bodies and Methods, filed Feb. 3, 2010. |
U.S. Appl. No. 12/824,070, Ramberg, Powertrain Controls, filed Jun. 25, 2010. |
U.S. Appl. No. 12/671,825, Ramberg, Porous Bodies and Methods, filed Aug. 9, 2010. |
U.S. Appl. No. 12/756,987, Ramberg, Substrate Fabrication, filed Apr. 8, 2010. |
U.S. Appl. No. 12/183,917, Ramberg, Porous Bodies and Methods, filed Jul. 31, 2008. |
U.S. Appl. No. 13/316,534, Ramberg, Porous Bodies and Methods, filed Dec. 11, 2011. |
U.S. Appl. No. 13/327,300, Ramberg, Porous Bodies and Methods, filed Dec. 15, 2011. |
U.S. Appl. No. 13/343,713, Ramberg, Aerodynamic Aftertreatment, filed Jan. 5, 2012. |
U.S. Appl. No. 13/171,489, Ramberg, Layered Structures, filed Jun. 29, 2011. |
U.S. Appl. No. 13/152,273, Ramberg, Methods, filed Jun. 3, 2011. |
U.S. Appl. No. 13/152,275, Ramberg, Porous Bodies and Methods, filed Jun. 3, 2011. |
U.S. Appl. No. 13/494,073, Ramberg, Porous Bodies and Methods, filed Jun. 12, 2012. |
U.S. Appl. No. 13/593,564, Ramberg, Substrate Fabrication, filed Aug. 24, 2012. |
U.S. Appl. No. 13/726,853, Ramberg, Porous Bodies and Methods, filed Dec. 25, 2012. |
U.S. Appl. No. 13/743,357, Ramberg, Powertrain Controls, filed Jan. 17, 2013. |
U.S. Appl. No. 14/220,146, Ramberg, Substrate Fabrication, filed Mar. 20, 2014. |
Office Action mailed May 10, 2013 U.S. Appl. No. 13/593,564. |
Office Action mailed May 16, 2012 in U.S. Appl. No. 12/756,987. |
Office Action mailed Jan. 9, 2012 U.S. Appl. No. 12/756,987. |
“Changing the Substrate Technology to met future Emission Limits”, Lorenzo Pace and Manuel Presti, Emitec gmbh, downloaded fromhttp://www.emitec.com/en/bibliothek-downloads/overview.html on Feb. 21, 2012. |
Metal Supported Catalysts for Large-Volume Engine Applications: From Designing to Recycling 4th AVL Large Engine Techdays May 5 & 6, 2010 Dr.-Ing. Raimund Müller Dipl.-Ing. Oswald Holz Dr.-Ing. Andreas Scheeder, EMITEC Gesellschaft für Emissionstechnologie mbH Emitec gmbh, downloaded fromhttp://www.emitec.com/en/bibliothek-downloads/overview.html on Feb. 21, 2012. |
“Application of PM-METALIT® and SCRi® Systems” Rolf Brück, Klaus Müller-Haas, Oswald Holz, Peter Hirth EMITEC Gesellschaft für Emissionstechnologie mbH Robert-Gilles Entlesberger,Thomas Cartus AVL List GmbH, downloaded from http://www.emitec.com/en/bibliothek-downloads/overview.html on Feb. 21, 2012. |
Development of an Integrated NOx an PM Reduction Aftertreatment System: SCRiTM for Advanced Diesel Engines. Michael Rice, Jan Kramer, Emitec Inc. Dr. Raimund Mueller, Klaus Mueller-Haas, Emitec GmbH, SAE World Congress, Apr. 2008, downloaded from http://www.emitec.com/en/bibliothek-downloads/overview.html on Feb. 21, 2012. |
Office Action mailed Jan. 11, 2013 U.S. Appl. No. 13/593,564. |
R-1 Direct Metal Printer product description, ProMetal (Ex-One) downloaded from www.exone.com Mar. 2009. |
S-15 3D printer product description, ProMetal RCT (Ex-One), downloaded from www.exone.com Mar. 2009. |
S-print product description, ProMetal RCT (Ex-One), downloaded from www.exone.com Mar. 2009. |
ASTM Test Procedure D7348-08, “Standard Test Methods for Loss on Ignition (LOI) of Solid Combustion Residues,” purchased from www.astm.org Aug. 30, 2011. |
Australian Office Action (summer 2012). |
WO 2008/121390 A1—cited in NoA , Oct. 2013—went National in US as U.S. Appl. No. 12/593,521 (so cited in US refs). |
Advisory Action mailed May 14, 2012 U.S. Appl. No. 12/699,736. |
Office Action mailed Feb. 13, 2012 in U.S. Appl. No. 12/699,736. |
Translation of EP-0337047, Oct. 1998 (DeBoodt) U.S. Appl. No. 12/699,736. |
Final Office Action mailed Apr. 29, 2013 U.S. Appl. No. 12/699,736. |
Specifiers Guide for Pervious Concrete Pavement Design, Version 1.2, Colorado Ready Mixed Concrete Association, Centennial, Co. Publication date unknown; downloaded from www.crmca.org Aug. 2009. |
Porous Silicon Nitride for Low Pressure Loss DPF, Hayashi, Ichiro; Shinohara, Nobuhiro; Watanabe, Toshinari; Takahashi, Hideo; Reports Res. Lab. Asahi Glass Col, Ltd., 56, pp. 25-27 (2005). |
Extrusion of Lightweight Construction Materials from Fly Ash, H.D. DeFord & G.P. Wirtz, Ceram. Eng. Sci. Proc. 14 [1-2] pp. 298-308 (1993). |
Characterization of glass ceramics made from incinerator fly ash, T.W. Cheng & Y. S. Chen, Ceramics International, 30, pp. 343-349 (2004). |
Characterization of α-cordierite glass-ceramics from fly ash, Yong He, Weimin Chang, Hesheng Cai, Journ. Hazardous Mat. B120, pp. 265-269 (2005). |
Cristobalite formation from thermal treatment of Texas lignite fly ash, M.Y.A. Mollah, S. Promreuk, R. Schennach, D.L. Cocke. R. Guler, Fuel, 78, pp. 1277-1282 (1999). |
Densification of ashes from a thermal power plant, E. Benavidez, C. Grasselli, N. Quaranta, Ceramics International, 29, pp. 61-68 (2003). |
Effect of borate addition on the sintered properties of pulverized fly ash, E.A. Uwe, A.R. Boccaccini, S.G. Cook, C.R. Cheeseman, Ceramics International, 33, pp. 993-999 (2007). |
Engineering and environmental properties of thermally treated mixtures containing MSWI fly ash and low-cost additives, A. Polettini, R. Pomi, L. Trinci, A. Muntoni, S. Lo Mastro, Chemosphere, 56, pp. 901-910 (2004). |
Flyash as Support for Ni Catalysts in Carbon Dioxide Reforming of Methane, S. Wang, G.Q. Lu, H. Y. Zhu, Chemistry Letters, pp. 385-386 (1999). |
Mineralogy and microstructure of sintered lignite coal fly ash, M. Ilic, C. Cheeseman, C. Sollars, J. Knight, Fuel, 82, pp. 331-336 (2003). |
Mullite ceramics derived from coal fly ash, J.S. Jung, H.C. Park, Stevens, Journ. Mat. Sci. Letters, 20, pp. 1089-1091 (2001). |
Physical-mechanical and environmental properties of sintered municipal incinerator fly ash, G. De Casa, T. Mangialardi, A. E. Paolini, L. Piga, Waste Management, 27, pp. 238-247 (2007). |
Processing and properties of a glass-ceramic from coal fly ash from a thermal power plant through an economic process, J. M. Kim, H, S. Kim, Journ. Europ. Ceram. Soc., 24, pp. 2825-2833 (2004). |
Sintering of a class F fly ash, J. J. Biernacki, A. K. Vazrala, H. W> Leimer, Fuel, 87, pp. 782-792 (2008). |
Synthesis of cordierite from fly ash and its refractory properties, Kumar, K.K. Singh, P. Ramachandrarao, Journ. Mat. Sci. Letters, 19, pp. 1263-1265 (2000). |
International Search Report and Written Opinion, prepared by KIPO for PCT/US2008/071793, “Porous Bodies and Methods” (Feb. 2009). |
Office Action mailed Jan. 25, 2012 U.S. Appl. No. 13/327,300. |
Machine translation of JP 2006004920 (Jan. 2006), Yasuda Masahiro; as provided by USPTO U.S. Appl. No. 13/327,300. |
Office Action mailed Jan. 26, 2012 U.S. Appl. No. 13/316,534. |
Response to Supplementary European Search Report associated with (European patent application No. 08 796 966.3-2113, which is the National Stage application associated with PCT/US08/71793, which is the related PCT application of U.S. Appl. No. 12/183,917, U.S. Appl. No. 12/671,825, and their child applications). |
Office Action mailed May 3, 2012 in U.S. Appl. No. 13/327,300. |
Machine Translation of JP 2002-24898 A (Nitta), published Sep. 3, 2002, as provided by USPTO (U.S. Appl. No. 13/327,300) May 3, 2012. |
Machine Translation of abstract of JP 2005-060159 A (Yamazaki), published Mar. 10, 2005, as provided by USPTO (U.S. Appl. No. 13/327,300) May 3, 2012. |
Grutzeck, et al., “Zeolites Synthesized from Class F Fly Ash and Sodium Aluminate Slurry” 1997, J. Am. Ceram. Soc., 80 [9] as provided by USPTO (U.S. Appl. No. 13/327,300) May 3, 2012. |
Wang et. Al., “Characterizing the Metal Absorption Capacity of a Class F Coal Fly Ash,” Environ. Sci., Technol., 2004, 38, 6710-6715, as provided by USPTO (U.S. Appl. No. 13/327,300) May 3, 2012. |
Office Action mailed Jun. 25, 2012 U.S. Appl. No. 12/671,825. |
“Flow in Microporous Silicon Carbide: an Experimental and Numerical Study” K. Gjendal & H.B. Madsen, M.S. Thesis, DTU (Denmark) Dec. 1, 2008. |
Office Action mailed Sep. 13, 2012 U.S. Appl. No. 13/494,073. |
Office Action mailed Sep. 4, 2012 U.S. Appl. No. 13/327,300. |
Office Action and translations received Dec. 28, 2012 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793). |
Partial translation of JPA—1988143913, as provided with Office Action received received Dec. 28, 2012 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793). |
Machine translation of JPA—1997025155, as provided with Office Action received received Dec. 28, 2012 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793). |
Machine translation of JPA—1996332330, as provided with Office Action received received Dec. 28, 2012 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793). |
Machine translation of JPA—19870363083, as provided with Office Action received received Dec. 28, 2012 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793). |
Office Action and counsel-provided translation received Jan. 16, 2013, issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Office Action mailed Feb. 1, 2013 U.S. Appl. No. 13/327,300. |
Communication pursuant to Article 94(3) EPC, downloaded from EPO register May 2, 2013, in associated European Patent Application No. 08 796 966. |
Final Office Action mailed Jun. 27, 2013 U.S. Appl. No. 13/327,300. |
Response to SIPO Office Action (PRC, China) for copending Chinese patent application No. 200880110124.8 filed Jun. 2013. |
Response to JPO Office Action (Japan) for copending Japanese patent application No. JP2010-520197 filed Jun. 2013. |
Office Action mailed Nov. 2, 2012 U.S. Appl. No. 12/699,736. |
Translation of EP EP 0337047 (DeBoodt, M) as provided by USPTO in Office Action mailed Nov. 2, 2012 U.S. Appl. No. 12/699,736. |
Office Action mailed Oct. 20, 2011 in U.S. Appl. No. 12/699,736. |
Supplementary European Search Report received from the European Patent Office for European Patent Application 08796966.3-2113/2180933 (PCT/US2008071793), which is related to PCT Patent Application No. PCT/US08/71793, U.S. Appl. No. 12/183,917 and their related applications. |
Office Action mailed Dec. 9, 2011 U.S. Appl. No. 12/671,825. |
An initial study of the fine fragmentation fly ash particle mode generated during pulverized coal combustion, W. S. Seames, Fuel Processing Technology, 81, pp. 109-125 (2003). |
Characterization of a glass-ceramic produced from thermal power plant fly ashes, M. Erol, A. Genc, M.L. Ovecoglu, E. Yucelen, S. Kucukbayrak, Y. Taptik, J. Europ. Ceram. Soc., 20, pp. 2209-2214 (2000). |
Characterization of the bottom ash in municipal solid waste incinerator, J. M. Chimenos, M. Segarra, M. A. Fernandez, F. Espiell, Journ. Hazard. Materials, A:64, pp. 211-222 (1999). |
Crystallization and properties of glasses prepared from Illinois coal fly ash, E. J. DeGuire, S. H. Risbud, J. Mat. Sci., 19, pp. 1760-1766 (1984). |
Commercially Useful By-Products of Coal Combustion, M. R. Gottschalk, J. R. Hellmann, B. E. Scheetz, Ceramic Transactions, vol. 119, pp. 125-134 (2001). |
Viscous Sintering of Coal Ashes. 2. Sintering Behavior at Short Residence Times in a Drop Tube Furnace, B. Jung & H. Schobert, Energy & Fuels, 6, pp. 59-68 (1992). |
Conversion to glass-ceramics from glasses made by MSW incinterator fly ash for recycling, Y.J. Park, J. Heo, Ceramics Int'l., 28, pp. 689-694 (2002). |
Ceramic Diesel Particulate Filters, J. Adler, Int. J. Appl. Ceram. Technol., 2 [6] pp. 429-439 (2005). |
Office Action mailed Dec. 21, 2010 U.S. Appl. No. 12/183,917. |
Machine translation of KR 2003002221 A, provided by USPTO with Office Action mailed Dec. 21, 2010 in U.S. Appl. No. 12/183,917, Jeong, In-Hwa, et al. (orig. cited as Chung H S et al.). |
Office Action mailed Jan. 2011 U.S. Appl. No. 12/671,825. |
Fabrication and Physical Properties of Honeycomb Type Cordierite Ceramic Filter Using Fly Ash; Sung-Jin Kim, et al., Journal of the Korean Ceramic Society, 43, 351-357 (2006) as provided by USPTO with Office Action mailed Jan. 2011 in U.S. Appl. No. 12/671,825. |
Mineral Sequestration of CO2 by aqueous carbonation of coal combustion fly ash; G. Montes-Hernandez et al., Journal of Hazardous Materials, 161, 1347-1354 (2008). |
Ash to Reduce Trace Element Mobility; T.A. Tawfic, Wyoming Water Resources Center (1995). |
Office Action mailed Jun. 13, 2011 in U.S. Appl. No. 12/671,825. |
Machine translation of JP 11029346, Yamamoto, Haruo, as provided by USPTO U.S. Appl. No. 13/152,275, Aug. 2011. |
Office Action mailed Aug. 12, 2011 in U.S. Appl. No. 13/152,273. |
Office Action mailed Aug. 12, 2011 in U.S. Appl. No. 13/152,275. |
Translation of abstract and front matter of KR 2003002221 A, as provided by USPTO U.S. Appl. No. 12/671,825, Chung, H.S., et al. |
Fabrication of Cordierite Honeycomb from Fly Ash; Sung-Jun Kim, et al., Materials Science Forum vols. 534-536 (2007) pp. 621-624; as provided by USPTO U.S. Appl. No. 12/671,825. |
Resubmission with additional pages (since previously submitted IDS) of machine translation of JP 2005-060159 A (Yamazaki), published Mar. 10, 2005, as provided by USPTO (U.S. Appl. No. 13/327,300) May 3, 2012. |
Response to Article 94(3) Communcation from European Patent Office in European Patent Application No. |
Office Action received Sep. 2013, issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Office Action received Sep. 2013 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793. |
Response submitted to IP Australia in Australian Patent Application No. 2008284107, which is the AU National stage of PCT/US2008/071793. |
Mechanical Translation of JP2005-034797A, Feb. 10, 2005. |
Response to Sep. 2013 Office Action issued by SIPO (China) in copending PRC (China) Pat. Appln. No. 200880110124.8, which is the National Stage of PCT/US2008/071793. |
Response to Office Action received Sep. 2013 in Japanese patent application JP2010-520197, which is the National Stage of PCT/US2008/071793. |
Communication pursuant to Article 94(3) EPC, downloaded from EPO register Feb. 11, 2014, in associated European Patent Application No. 08 796 966. |
Number | Date | Country | |
---|---|---|---|
61167857 | Apr 2009 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13593564 | Aug 2012 | US |
Child | 14220146 | US | |
Parent | 12756987 | Apr 2010 | US |
Child | 13593564 | US |