BRPI0911165B1 - A process for converting a carbonaceous material into a desired product comprising one or more hydrocarbons or one or more alcohol. - Google Patents

Description

"PROCESS FOR CONVERTING CARBONIDE MATERIAL INTO A DESIRED PRODUCT UNDERSTANDING ONE OR MORE HYDROCARBONS OR ONE OR MORE ALCOHOL" This application claims priority in accordance with 35 USC §119 (e) to US provisional application serial number 61 / 043.465, filed on April 9, 2008, provisional application US serial number 61 / 104,432, filed on October 10, 2008, and provisional application US serial number 61 / 152,645, filed on February 13, 2009. These prior applications are incorporated. here by reference.

Technical Field The present invention relates to a process for benefiting carbonaceous materials using microchannel process technology. The process may be used to convert a carbonaceous material (e.g. biomass, solid waste, etc.) into one or more hydrocarbons or alcohols. Hydrocarbons and alcohols may be used as synthetic fuels.

Background The US military uses billions of gallons of petroleum-based fuels annually. Transporting these fuels to remote military bases is expensive and time consuming, and the fuel is often a prime target for terrorists. The problem, therefore, is to provide fuel sources and more dryness.

Summary The present invention provides a solution to this problem. The present invention relates to a process for converting carbonaceous materials such as biomass, solid waste and the like into hydrocarbons and alcohols that can be used as synthetic fuel (e.g. automotive fuel, diesel fuel, aviation fuel, etc.). The inventive process employs the use of microchannel reactors that are compact and easily transportable. As such, the inventive process can be adapted for use on equipment that can be easily transported to remote locations such as military bases and the like. With the inventive process it is possible to convert waste products generated on such military bases into fuels such as automotive fuel, diesel fuel, aviation fuel and the like. For example, the inventive process may be adapted to produce approximately 50 to about 500 barrels per day of synthetic fuel on such a basis. The inventive process may also be adaptable for use with larger scale operations where sources of carbonaceous material such as municipal solid waste are converted into products useful as synthetic fuel. The present invention relates to a process for converting a carbonaceous material into a desired product comprising one or more hydrocarbons or one or more alcohols, the process comprising: (A) gasifying the carbonaceous material at a temperature of at least about 700 ° C. to form synthesis gas; and (B) flowing the synthesis gas into a microchannel reactor in contact with a catalyst to convert the synthesis gas into the desired product. The products have various uses including use as synthetic fuels.

Brief Description of the Drawings In the accompanying drawings similar parts and characteristics have similar references. Several drawings are schematic illustrations that may not necessarily be drawn to scale. Figure 1 is a flowchart illustrating the inventive process in a specific form, the process comprising converting a carbonaceous material into one or more hydrocarbons or one or more alcohols using a gasifier in combination with an Fischer-Microchannel or microchannel reactor. Tropsch (FT). The carbonaceous material is converted to synthesis gas in the gasifier. The synthesis gas is converted to one or more hydrocarbons or alcohols in the microchannel reactor. Figure 2 is a flow chart of a process that is the same as the process shown in Figure 1 except that steam, which is used as a heat exchange fluid in the microchannel reactor, is also used as a gasifier in the gasifier. . Figure 3 is a flowchart of a process that is the same as the process illustrated in Figure 1 except that the process includes the use of a nitrogen separator upstream of the gasifier. Nitrogen is separated from air in the nitrogen separator. The remaining oxygen is used as the gasifying agent in the gasifier. Figure 4 is a flowchart of a process that is the same as the process shown in Figure 1 except that the process shown in Figure 4 employs the use of a pyrolysis reactor. The carbonaceous material is converted to pyrolytic oil in the pyrolysis reactor. Pyrolytic oil is used as the carbonaceous feed for the gasifier. Figure 5 is a flowchart of a process that is the same as the process shown in Figure 4 except that liquid hydrocarbons such as tar are separated from the synthesis gas flowing out of the gasifier and recycled to the pyrolysis reactor. Fig. 6 is a flow chart of a process employing the use of the microchannel gasifier and reactor illustrated in Fig. 1 in combination with a vapor methane reforming microchannel (SMR) reactor. The SMR microchannel reactor is used to convert waste gas flowing out of the microchannel reactor into synthetic gas that is recycled to the microchannel reactor. Figure 7 is a flow chart of a process that is the same as the process shown in Figure 6 except that carbon dioxide is separated from the syngas gas flowing out of the gasifier. The resulting low carbon dioxide synthesis gas then flows into the microchannel reactor. Figure 8 is a flow chart of a process that is the same as the process shown in Figure 7 except that carbon dioxide that is separated from the synthesis gas flowing out of the gasifier flows into the SMR microchannel reactor where it is combined with waste gas from the microchannel reactor and converted to synthesis gas. Figure 8A is a process flowchart that is the same as the process illustrated in Figure 1 where the microchannel reactor is a Fischer-Tropsch microchannel reactor except that the product flowing out of the Fischer-Tropsch microchannel reactor is subjected to a hydrocracking reaction in a hydrocracking microchannel reactor.

Figures 9 and 10 are schematic illustrations of a container used to house a plurality of Fischer-Tropsch or microchannel reactors, or a plurality of SMR microchannel reactors, or a plurality of hydrocracking microchannel reactors. In Figures 9 and 10, five alcohol-forming or Fischer-Tropsch microchannel reactors, five SMR microchannel reactors, or five hydrocracking microchannel reactors are shown.

Figures 11-14 are schematic illustrations of repeating units that may be used in the Fischer-Tropsch alcohol-forming microchannel reactors. Each of the repeating units illustrated in Figures 11-14 includes an Fischer-Tropsch alcohol-forming process microchannel containing a reaction zone containing a catalyst and adjacent heat exchange channels. Heat exchange fluid flowing in the heat exchange channels illustrated in Figure 11 flows in a direction that is cross-current with respect to the flow of process fluids in the Fischer-Tropsch or alcohol-forming process microchannel. The heat exchange fluid flowing in the heat exchange channel illustrated in Figure 12 may flow in a direction that is co-current or countercurrent to the process fluid flow in the alcohol-forming process or Fischer-Tropsch microchannel. The heat exchange channels illustrated in Figures 13 and 14 provide the heat exchange fluid flow in a direction that is cross-current with respect to the process fluid flow in the Fischer-Tropsch or alcohol-forming process channels. The heat exchange channels illustrated in Figures 13 and 14 provide heat exchange zones that cover only part of the length of the reaction zones in the Fischer-Tropsch alcohol forming process channels. Molded heat exchange profiles can be provided with each of these modalities by controlling the number of heat exchange channels in thermal contact with different sections of the process microchannels. With these molded heat exchange profiles more cooling channels can be provided in some parts of process microchannels compared to other parts of process microchannels. For example, more cooling channels may be provided at or near reaction zone inlets compared to downstream parts of the reaction zones. The heat exchange profile can be shaped by controlling the heat exchange fluid flow rate in the heat exchange channels. For example, a relatively high heat exchange fluid flow rate in the heat exchange channels in thermal contact with the inlets for the reaction zones may be used in combination with relatively low heat exchange fluid flow rates in heat exchange channels in thermal contact with sections downstream of reaction zones.

Figures 15-20 are schematic illustrations of catalysts or catalyst supports that may be used in the SMR process microchannels, combustion channels or Fischer-Tropsch process microchannels. The catalyst illustrated in Fig. 15 is in the form of a particulate solids bed. The catalyst illustrated in Fig. 16 has a flow drawing. The catalyst illustrated in Figure 17 is a direct flow structure. Figures 18-20 are schematic illustrations of fin assemblies that may be used to support the catalyst.

Figures 21-25 are schematic illustrations of microchannel repeat units that may be used in the SMR microchannel reactor. Each of these repeating units comprises a combustion channel and one or more SMR process microchannels. The combustion channels illustrated in figures 21-25 include stage addition channels to flow oxygen or an oxygen source into the combustion channels. Figure 21 illustrates an upside-down U-shape SMR process microchannel adjacent to an M-shape combustion channel. Figure 22 shows a single SMR process microchannel adjacent to an M-shape combustion channel. Figure 23 illustrates two SMR process microchannels and an M-shape combustion channel, one of the SMR process microchannels being adjacent to the M-shape combustion channel and the other SMR process microchannel being adjacent to the first cited SMR process microchannel , both SMR process microchannels being in thermal contact with the combustion channel. Figure 24 illustrates a single combustion channel, a staged addition channel positioned on one side of the combustion channel and an SMR process channel positioned on the other side of the combustion channel. Fig. 25 illustrates a repeating unit that is similar to the repeating unit illustrated in Fig. 24 except that the SMR process microchannel in the repeating unit illustrated in Fig. 25 is shaped like a U-shaped microchannel upside down. low. In Figures 21-25 the channels are illustrated as being spaced apart for clarity, however, in actual practice the channels would be stacked on top of each other or positioned side by side without spacing between the channels. Channels can share common walls on channel interfaces.

Figures 26 and 27 are schematic illustrations of surface features that may be used in the channels employed in the Fischer-Tropsch alcohol-forming microchannel reactor and / or the SMR microchannel reactor used in the inventive process. Figure 28 is a flowchart of the process described in example 1. Figure 29 is a schematic illustration of the microchannel reactor described in example 2. Figure 30 is a schematic illustration of a waveform used to make the microchannel reactor described in example 2.

Detailed Description All ranges and ratio limits disclosed in the specification and claims may be combined in any way. It should be understood that unless specifically stated otherwise, references to "one", "one" and / or "the" may include one or more of one, and that reference to a singular item may also include the plural item. All combinations specified in the claims may be combined in any way. The term "microchannel" may refer to a channel having at least an internal dimension of height or width of up to approximately 10 mm (mm), and in an embodiment up to approximately 5 mm, and in an embodiment up to approximately 2 mm, and in up to approximately 1 mm. The microchannel may comprise at least one inlet and at least one outlet wherein at least one inlet is distinct from at least one outlet. The microchannel may not be merely a hole. The microchannel may not be merely a channel through a zeolite or mesoporous material. The length of the microchannel may be at least about twice the height or width, and in a mode at least about five times the height or width, and in a mode at least about ten times the height or width. The internal height or width of the microchannel may be in the range of from about 0.05 to about 10 mm, and in an embodiment of from about 0.05 to about 5 mm, and in an embodiment of from about 0.05 to about 2 mm, and in an embodiment of approximately 0.05 to approximately 1.5 mm, and in an embodiment of approximately 0.05 to approximately 1 mm, and in an embodiment of approximately 0.05 to approximately 0.75 mm, and in an embodiment of approximately 0.05 to approximately 0.5 mm. The other internal dimension of height or width may be of any dimension, for example up to approximately 3 meters, and in one embodiment approximately 0.01 to approximately 3 meters, and in one embodiment approximately 0.1 to approximately 3 meters. The length of the microchannel may be of any size, for example, up to about 10 meters, and in an embodiment of from about 0.1 to about 10 meters, and in an embodiment of from about 0.2 to about 10 meters, and in an embodiment. approximately 0.2 to approximately 6 meters, and in a mode of approximately 0.2 to approximately 3 meters. The microchannel may have a cross section having any shape, for example a square, rectangle circle, semicircle, trapezoid, etc. The shape and / or size of the microchannel cross section may vary with respect to its length. For example, the height or width may taper from a relatively large dimension to a relatively small dimension, or vice versa, relative to the length of the microchannel. The term "microchannel reactor" may refer to equipment comprising one or more process microchannels where a reaction process is performed. The process may be an alcohol-forming or Fischer-Tropsch reaction process or an SMR reaction process. When two or more process microchannels are used, the process microchannels may be operated in parallel. The microchannel reactor may include a manifold or tubing assembly to provide fluid flow into one or more process microchannels, and a footer or tubing assembly that provides fluid flow out of one or more process microchannels . The microchannel reactor may comprise one or more heat exchange channels adjacent to and / or in thermal contact with one or more process microchannels. Heat exchange channels provide heating and / or cooling to the fluids in the process microchannels. When used in the SMR microchannel reactor, the heat exchange channels may be combustion channels. Heat exchange channels and / or combustion channels may be microchannel. The microchannel reactor may include a manifold or tubing assembly to provide heat exchange fluid flow into the heat exchange channels, and a footer or tubing assembly that provides heat exchange fluid flow out of the heat exchange channels. The term "process microchannel" may refer to a microchannel where a process is performed. The process may refer to performing an Fischer-Tropsch (FT) alcohol formation reaction or an SMR reaction. The term "volume" with respect to volume in a process microchannel may include any volume in the process microchannel a process fluid may flow through or flowby. This volume may include volume in the surface characteristics that may be positioned in the process microchannel and adapted for fluid flow in either a direct flow mode or a flow mode. The term "adjacent" when referring to the position of one channel relative to the position of another channel may mean directly adjacent such that a wall or walls separate the two channels. In one embodiment, both channels may have a common wall. The common wall may vary in thickness. However, "adjacent" channels may not be separated by an intermediate channel that may interfere with heat transfer between the channels. A channel may be adjacent to another channel about only part of the size of the other channel. For example, a process microchannel may be longer than and extend beyond one or more adjacent heat exchange channels. The term "thermal contact" may refer to two bodies, for example, two channels, which may or may not be in physical contact with or adjacent to one another, but still exchange heat with one another. A body in thermal contact with another body may heat or cool the other body. The term "fluid" may refer to a gas, a liquid, a mixture of gas and liquid, or a gas or liquid containing dispersed solids, liquid droplets and / or gas bubbles. The droplets and / or bubbles may be irregularly or regularly shaped and may be of similar or different sizes.

The terms "gas" and "steam" may have the same meaning and are sometimes used interchangeably. The term "residence time" or "average residence time" may refer to the internal volume of a space in a channel occupied by a fluid flowing in space divided by the average volumetric flow rate for fluid flowing in space at temperature. and pressure being used.

The terms "upstream" and "downstream" may refer to positions in a channel (for example, a process microchannel) or in a process flowchart that is relative to the flow direction of a fluid in the process channel or flowchart. . For example, a position in a process channel or flowchart not yet reached by a portion of a fluid flow flowing toward that position would be downstream of that portion of the fluid flow. A position in the process channel or flow chart already passed through a portion of a fluid flow flowing away from that position would be upstream of that portion of the fluid flow. The terms "upstream" and "downstream" do not necessarily refer to a vertical position since the channels used herein may be oriented horizontally, vertically or at an inclined angle. The term "wedge" may refer to a flat or substantially flat plate or sheet. The thickness of the wedge may be the smallest dimension of the wedge and may be up to approximately 4 mm, and in one embodiment in the range of approximately 0.05 to approximately 2 mm, and in one embodiment in the range of approximately 0.05 to approximately 1 mm. , and in an embodiment in the range from about 0.05 to about 0.5 mm. The wedge can be any length and width. The term "surface feature" may refer to a depression in a channel wall and / or a projection from a channel wall that disrupts the flow within the channel. Examples of surface feature drawings that may be used are illustrated in Figures 26 and 27. Surface features may be in the form of circles, spheres, trunks, oblong, squares, rectangles, slanted rectangles, locks, borders, vanes, airfoils, wavy shapes, and the like and combinations of two or more thereof. Surface features may contain sub-features when the larger walls of the surface features still contain minor surface features that may be in the form of notches, waves, grooves, holes, burrs, locks, cutouts, and the like. Surface features may have a depth, a width and for non-circular surface features a length. Surface features may be formed on or on one or more of the interior walls of the process microchannels, heat exchange channels and / or combustion channels used in accordance with the disclosed process. Surface characteristics may be referred to as passive surface characteristics or passive mixture characteristics. Surface features can be used to disrupt flow (eg, disrupt laminar flow lines) and create advective flow at an angle to the volume flow direction. The term "heat exchange channel" may refer to a channel having a heat exchange fluid therein which provides heat and / or absorbs heat. The heat exchange channel may absorb heat from or supply heat to an adjacent channel (e.g., process microchannel) and / or one or more channels in thermal contact with the heat exchange channel. The heat exchange channel may absorb heat from or provide heat to channels that are adjacent to each other but not adjacent to the heat exchange channel. In one embodiment, one, two, three or more channels may be adjacent to each other and positioned between two heat exchange channels. The term "heat transfer wall" may refer to a common wall between a process microchannel and an adjacent heat exchange channel where heat transfers from one channel to another through the common wall. The term "heat exchange fluid" may refer to a fluid that can release heat and / or absorb heat.

The term "waveform" may refer to an adjoining piece of thermally conductive material that is transformed from a flat object to a three-dimensional object. The waveform may be used to form one or more microchannels. The waveform may comprise a right angle corrugated insert that may be nested between opposing flat sheets or wedges. The right angle corrugated insert may have rounded edges. Thus one or more microchannels can be defined on three sides by the waveform and on the fourth side by one of the flat sheets or wedges. The waveform may be made of any of the thermally conductive materials disclosed herein as being useful for making the microchannel reactor. These may include copper, aluminum, stainless steel and the like. The thermal conductivity of the waveform may be approximately 1 W / m-K or higher. The term "volume flow direction" may refer to the vector through which fluid may travel in an open path in a channel. The term "volume flow region" may refer to open areas in a microchannel. A contiguous volume flow region can allow rapid fluid flow through a microchannel without significant pressure drops. In one embodiment, the flow in the volume flow region may be laminar. A volume flow region may comprise at least about 5% of the internal volume and / or cross-sectional area of a microchannel, and in an embodiment of from about 5% to approximately 100% and in an embodiment of from approximately 5% to approximately 99. % and about 5% to about 95% mode, and about 5% to about 90% mode and about 30% to about 80% mode of internal volume and / or microchannel cross-sectional area .

The terms "open channel" or "flow channel" or "open path" may refer to a channel (e.g. a microchannel) with a gap of at least approximately 0.01 mm that extends all the way through the channel of such a channel. so that fluid can flow through the channel without finding a barrier to flow. The clearance can extend up to approximately 10 mm. The term "cross-sectional area" of a channel (e.g., process microchannel) may refer to a measured area perpendicular to the direction of fluid volume flow in the channel and may include all areas in the channel including any surface features that may be present but does not include channel walls. For channels that curve along their length, the cross-sectional area can be measured perpendicular to the volume flow direction at a selected point along a line that is parallel to the length and is in the center (per area) of the channel. Height and width dimensions can be measured from one channel wall to the opposite channel wall. These dimensions may not be changed by applying a coating to the wall surface. These dimensions may be average values that account for variations caused by surface characteristics, surface roughness, and the like. The term "open cross-sectional area" of a channel (e.g., process microchannel) may refer to an open area for volume fluid flow in a measured channel perpendicular to the direction of fluid flow volume flow in the channel. . The open cross-sectional area may not include internal obstructions such as surface features and the like that may be present. The term "surface velocity" for the velocity of a fluid flowing in a channel may refer to the velocity resulting from dividing the volumetric flow rate of the fluid into the inlet temperature and pressure of the channel divided by the cross-sectional area of the channel. The term "free flow velocity" may refer to the velocity of a flow that flows into a channel at a sufficient distance from the sidewall of the channel such that the velocity is at a maximum value. The velocity of a flow flowing through a channel is zero in the sidewall if a no-slip condition is applicable, but increases as the distance from the sidewall increases until a constant value is obtained. This constant value is the "free flow speed." The term "process fluid" may be used herein to refer to reagents, product and any diluent or other fluid that may flow into a process microchannel. The term "reaction zone" may refer to the space in a microchannel where a chemical reaction occurs or in which a chemical conversion of at least one species occurs. The reaction zone may contain one or more catalysts. The term "yield" may refer to the number of moles of product leaving a microchannel reactor divided by the number of moles of a reagent entering the microchannel reactor. The term "cycle" may refer to a single passage of reagents through a microchannel reactor. The term "graduated catalyst" may refer to a catalyst with one or more gradients of catalytic activity. The graduated catalyst may have a varying concentration or surface area of a catalytically active metal. The graduated catalyst may have a variable rate of motion of catalytically active sites. The graduated catalyst may have physical properties and / or a shape that varies as a function of distance. For example, the graduated catalyst may have an active metal concentration that is relatively low at the inlet to a process microchannel and increases at a higher concentration near the outlet of the process microchannel, or vice versa; or a lower concentration of catalytically active metal closer to the center (i.e. midpoint) of a process microchannel and a higher concentration closer to a process microchannel wall, or vice versa, etc. The thermal conductivity of a graduated catalyst may vary from one location to another in a process microchannel. The surface area of a graduated catalyst may be varied by varying the size of catalytically active metal sites on a constant surface area support, or by varying the surface area of the support such as by varying the support type or particle size. A graduated catalyst may have a porous support where the surface area to support volume ratio is higher or lower in different parts of the process microchannel followed by applying the same catalyst coating everywhere. A combination of two or more of the above embodiments may be used. The graduated catalyst may have a single catalytic component or multiple catalytic components (for example, a bimetallic or trimetal catalyst). The graduated catalyst may change its properties and / or composition gradually as a function of distance from one location to another in a process microchannel. The graduated catalyst may comprise rimmed particles having catalytically active metal "eggshell" distributions in each particle. The graduated catalyst may be graduated in the axial direction along the length of a process microchannel or in the lateral direction. The graduated catalyst may have different catalyst compositions, different charges and / or numbers of active catalytic sites that may vary from one position to another in a process microchannel. The number of catalytically active sites can be changed by altering the porosity of the catalytic structure. This can be accomplished using a wash coating process that deposits varying amounts of catalytic material. An example may be the use of different porous catalyst thicknesses along the process microchannel length, whereby a thicker porous structure may be left where more activity is required. A change in porosity to a fixed or variable porous catalyst thickness may also be used. A first pore size may be used adjacent to an open area or clearance for flow and at least a second pore size. may be used adjacent to the process microchannel wall. The term "biomass" may refer to living and recently dead biological material that may be used as a fuel. The term biomass may refer to plant matter grown for use as biofuel. The term biomass may include animal or plant matter for the production of fibers, chemicals or heat. Biomass may include biodegradable waste that can be burned as fuel. Biomass may comprise plants such as fast growing grass, hemp, corn, poplar, willow, sugar cane, oil palm and the like. The term "animal char" can refer to a solid material that remains after gases have been expelled or released from a carbonaceous material. Char can be formed during the combustion of a carbonaceous material. The term "tar" may refer to a viscous black liquid derived from the destructive distillation of a carbonaceous material. The term "gray" may refer to the solid residue that remains after a carbonaceous material is burned. The term "chain growth" may refer to growth in a molecule resulting from a reaction in which the molecule grows with the addition of new molecular structures (for example, the addition of methylene groups to a hydrocarbon chain in a synthesis of Fischer-Tropsch). The term "hydrocarbon" may refer to purely hydrocarbon compounds; that is, aliphatic compounds (e.g. alkane, alkene or alkine), alicyclic compounds (e.g. cycloalkane, cycloalkylene), aromatic compounds, alicyclic and aliphatic substituted aromatic compounds, aromatic substituted aliphatic compounds, aromatic substituted alicyclic compounds, and the like . Examples may include methane, ethane, propane, cyclohexane, ethyl cyclohexane, toluene, ethyl benzene, etc. the term "hydrocarbon" may refer to substituted hydrocarbon compounds; that is, hydrocarbon compounds containing non-hydrocarbon substituents. Examples of non-hydrocarbon substituents may include hydroxyl, acyl, nitro, etc. the term "hydrocarbon" may refer to hetero substituted hydrocarbon compounds; that is, hydrocarbon compounds that contain different carbon atoms in a chain or ring otherwise containing carbon atoms. Heteroatoms may include, for example, nitrogen, oxygen, sulfur and the like. The hydrocarbon compound may comprise approximately 10 carbon atoms or more for each non-hydrocarbon or heteroatom substituent. The term "higher molecular weight hydrocarbon" may refer to a hydrocarbon having 2 or more carbon atoms, and in one embodiment 3 or more carbon atoms, and in one embodiment 4 or more carbon atoms, and in one embodiment 5 or more carbon atoms, and in one embodiment 6 or more carbon atoms. Higher molecular weight hydrocarbons may have up to approximately 100 carbon atoms, and in one embodiment up to approximately 90 carbon atoms, and in one embodiment up to approximately 80 carbon atoms, and in one embodiment up to approximately 70 carbon atoms, and in one embodiment up to approximately 60 carbon atoms, and in one embodiment up to approximately 50 carbon atoms, and in one embodiment up to approximately 40 carbon atoms, and in one embodiment up to approximately 30 carbon atoms. The higher molecular weight hydrocarbons may be aliphatic hydrocarbons. Examples may include ethane, propane, butane, pentane, hexane, octane, decane, dodecane and the like. The term "Fischer-Tropsch" or "FT" may refer to a chemical reaction represented by the equation: N CO + 2n H2 -> (CH2) n + n H20 This reaction is an exothermic reaction that can be conducted in the presence of a Fischer-Tropsch catalyst. n can be any number, for example from 1 to about 10, and in a mode of 2 to about 10, and in a mode of 2 to about 8. The term "Fischer-Tropsch product" or "FT product" may be refer to a hydrocarbon product made by a Fischer-Tropsch process. The FT product may have a boiling point at or above approximately 30 ° C at atmospheric pressure. The term "FT waste gas" may refer to a gaseous product made by a Fischer-Tropsch process. The waste gas may have a boiling point below approximately 30 ° C at atmospheric pressure. The term "alcohol formation reaction" may refer to the synthesis reaction represented by the equation: n CO + H2 -> CnH2n + i OH + (n-1) H2 O This reaction is an exothermic reaction that can be conducted in the presence of an alcohol-forming catalyst may not be any number, for example from 1 to about 10, and in a mode of 2 to about 10, and in a mode of 2 to about 8. The term "Co-loading", may refer to the weight of Co in a catalyst divided by the total weight of the catalyst, that is, the total weight of Co plus any co-catalyst or promoter as well as any support. If the catalyst is supported on a support structure constructed as a foam, felt, padding or fin, the weight of such a constructed support structure cannot be included in the calculation. Similarly, if the catalyst is adhered to a channel wall, the weight of the channel wall may not be included in the calculation. The term "steam methane reforming" or "SMR" may refer to the reaction: H20 + CH4 -> CO + 3 H2 This reaction is endothermic, and may be conducted in the presence of an SMR catalyst. Δ CO + H2 product mixture may be referred to as synthesis gas or sin gas. The heat required to effect this reaction may be provided by the combustion reaction of a mixture of a fuel (eg H2) and oxygen or an oxygen source (eg oxygen enriched air or air). The combustion reaction is exothermic and may be conducted in the presence of a combustion catalyst. The term "hydrocracking process" refers to a process wherein one or more C-C bonds in a hydrocarbon reagent are disrupted to provide a product comprising two or more hydrocarbon products having lower molecular weights than the hydrocarbon reagent. For example, a C12 alkane may be converted to a C7 alkane and a C5 alkane. The term "mm" may refer to millimeter. The term "nm" may refer to nanomer. The term "MS" may refer to milliseconds. The term "ps" may refer to microseconds. The term "pm" may refer to micron or micrometer. The terms "micron" and "micrometer" have the same meaning and can be used interchangeably. Unless otherwise stated, all pressures are expressed in terms of absolute pressure. The carbonaceous material that may be used in the inventive process may comprise any carbon or organic containing material which may be gasified to produce synthesis gas. The carbonaceous material may comprise a food resource such as corn, soy and the like. The carbonaceous material may comprise a nonfood resource. The non-food resource can be mentioned as a second generation biofuel. The non-food resource may comprise any carbonaceous material not generally used as food. The unfeeded resource may be mentioned as a nonfood carbonaceous material. Examples of non-food carbonaceous materials that may be used may comprise coal (e.g., low grade coal, high grade coal and the like) oil (e.g. crude oil, heavy oil, tar sand oil, and the like) , biomass, solid waste, or a mixture of two or more thereof. Non-food carbonaceous material may comprise municipal solid waste (MSW), hazardous waste, waste-derived fuel (RDF), tires, petroleum coke, waste, debris, biogas from a digester, sewage sludge, animal waste (for example , chicken manure, turkey manure, cow manure, horse manure, as well as other animal waste), agricultural waste, corn fodder, fast-growing grass, wood, wood chips, grass clippings, demolition materials construction materials, plastic materials (eg plastic waste), cotton gin waste, landfill gas, natural gas, and the like. The nonfood carbonaceous material may comprise polyethylene or polyvinyl chloride. Mixtures of two or more of the above may be used. The carbonaceous material may be in the form of relatively large solid pieces and prior to step (A) such relatively large pieces may be minced into smaller pieces using, for example, a drill. The carbonaceous material may comprise water, and in at least one embodiment of the invention it may be advantageous to remove some or all of the water prior to the gasification step (Δ) of the inventive process. This can be accomplished using conventional drying techniques. The term "synthetic gas" refers to a gas mixture containing CO and H2. Synthesis gas is sometimes mentioned as singas. The synthesis gas which is formed in the gasification step (A) of the inventive process may comprise a gas mixture containing varying amounts of CO and H2. In at least one embodiment of the inventive process, it is advantageous to use a synthesis gas during step (B) with a H2 to CO molar ratio which may be in the range of approximately 0.5 to approximately 4, and in one embodiment in the range. from about 1 to about 3, and in a mode in the range from about 1.5 to about 2.5, and in a mode in the range from about 1.8 to about 2.2. If the amount of H2 produced during step (Δ) is not sufficient to provide the H2 to CO ratio specified above, additional amounts of H2 may be added to the synthesis gas prior to step (B) of the inventive process. The synthesis gas may also contain varying amounts of CO2 and water as well as particulate solids and other contaminants. CO2, water, particulate solids and other contaminants may be separated, or at least substantially separated from the synthesis gas, prior to performing step (B) of the inventive process. The inventive process, in its illustrated embodiments, will be described initially with reference to figures 1-8. Referring to Figure 1, process 100 employs the use of gasifier 110 and microchannel reactor 200. Microchannel reactor 200 may be referred to as a Fischer-Tropsch microchannel reactor when employed to convert synthesis gas into one or more hydrocarbons. Microchannel reactor 200 may be referred to as an alcohol-forming microchannel reactor when used to convert synthesis gas into one or more alcohols. In operation, the carbonaceous material enters the carbonator 110 through line 112. A gasifying agent (eg, steam, oxygen and / or air) enters the carbonator 110 through line 114. In carbonator 110, the carbonaceous material and agent Gasification gases are heated and subjected to a gasification reaction to form synthesis gas. Synthesis gas flows from aerator 110 into microchannel reactor 200 through line 116. Synthesis gas flowing out of aerator 110 may be at an elevated temperature, for example, above about 700 ° C, and as such. it may be advantageous to reduce the temperature of the synthesis gas prior to entering the microchannel reactor 200. This temperature is comparable to the desired operating temperature in the microchannel reactor 200 as discussed below using one or more heat exchangers in the line between gasifier 110 and the microchannel reactor 200. These heat exchangers may be microchannel heat exchangers. Synthesis gas flowing out of aerator 110 may contain undesirable levels of water, particulate solids, contaminants (eg sulfur, halogen, selenium, phosphorus, arsenic, nitrogen, carbon dioxide, and the like). Their concentrations may be reduced by using one or more liquid-gas sorption devices (which may employ the use of one or more ionic liquid sorbents), temperature oscillation adsorption devices (TSA), temperature oscillation adsorption devices or pressure (PSA), microchannel devices containing nanofiber layers or nanocomposite films, cyclones, capacitors, and the like, on the line between gasifier 110 and microchannel reactor 200. In microchannel reactor 200, syneresis gas flows through a or more process microchannels in contact with a catalyst to form the desired product. The catalyst may be a Fischer-Tropsch catalyst and the product formed by the Fischer-Tropsch catalyst contact may comprise one or more hydrocarbons. Alternatively, the catalyst may be an alcohol-forming catalyst and the product resulting from catalyst contact may comprise one or more alcohols. These two reactions are exothermic reactions.

These reactions may be controlled using a heat exchange fluid flowing through the microchannel reactor 200 as indicated by arrows 204 and 206. In one embodiment, the heat exchange fluid comprises steam. The resulting product flows out of microchannel reactor 200 through line 202. Process 110A shown in Figure 2 is the same as process 100 shown in Figure 1 except that steam, which is used as the heat exchange fluid In the microchannel reactor 200 it is also used as the gasifying agent in the gasifier 110. Steam flows from the microchannel reactor 200 through line 206 to the gasifier 110. In the gasifier 110, the steam functions as a gasifying agent during gasification of carbonaceous material. Process 100B shown in Fig. 3 is the same as process 100 shown in Fig. 1 except that process 100B includes a nitrogen separator 300. Nitrogen separator 300 may comprise any suitable device for separating nitrogen from air. For example, nitrogen separator 300 may comprise an ionic liquid separator, a temperature swing adsorption device (TSA) or a pressure swing adsorption device (PSA). In operation, air enters nitrogen separator 300 through line 302 where it undergoes a separation process with nitrogen being separated from air. This results in the formation of oxygen enriched air or purified oxygen. Nitrogen flows out of nitrogen separator 300 through line 304. Purified oxygen or oxygen enriched air flows from nitrogen separator 300 through line 114 into gasifier 110. Purified oxygen or oxygen enriched air works as a gasifying agent in the gasifier 110. The carbonaceous material and the gasifying agent are subjected to a gasification reaction to form synthesis gas. Synthesis gas flows from gasifier 110 through line 116 to microchannel reactor 200 where it is subjected to a reaction to form one or more hydrocarbons or one or more alcohols as discussed above. Process 100C shown in Fig. 4 is the same as process 100 shown in Fig. 1 except that Process 100C employs the use of pyrolysis reactor 400. In operation, the carbonaceous material enters pyrolysis reactor 400 through line 112. In the pyrolysis reactor 400, the carbonaceous material undergoes a pyrolysis reaction with the result being the formation of a pyrolytic oil. Pyrolytic oil flows from pyrolysis reactor 400 through line 402 to gasifier 110. A gasifying agent enters gasifier 110 through line 114. In gasifier 110, pyrolytic oil and gasifying agent are heated and subjected. to a gasification reaction to form synthesis gas. Synthesis gas flows from gasifier 110 through line 116 to microchannel reactor 200 where it undergoes a reaction to form one or more hydrocarbons or one or more alcohols as described above. Process 100D shown in Fig. 5 is the same as process 100C shown in Fig. 4 except that liquid hydrocarbons such as tar are separated from the synthesis gas flowing out of gasifier 110. These liquid hydrocarbons are recycled back to the pyrolysis reactor 400 from line 116 through line 118. The recycled liquid hydrocarbons and carbonaceous material entering the pyrolysis reactor 400 through line 112 are combined and pyrolised into the pyrolysis reactor 400 resulting in oil formation. pyrolytic. Pyrolytic oil flows from pyrolysis reactor 400 through line 402 to gasifier 110 where it is combined with a gasification agent entering gasifier 110 through line 114. Pyrolytic oil and gasification agent are heated in gasifier 110 and undergo a gasification reaction to form a synthesis gas. Synthesis gas flows from gasifier 110 through line 116 to microchannel reactor 200. In microchannel reactor 200, the synthesis gas is converted to one or more hydrocarbons or one or more alcohols as described above. Process 100E illustrated in Figure 6 employs the use of aerator 110 and microchannel reactor 200 discussed above in combination with a vapor methane reforming microchannel (SMR) reactor 500. In the SMR 500 microchannel reactor, an SMR reaction is conducted. where a waste gas comprising methane reacts with steam in an endothermic reaction to form synthesis gas. The SMR microchannel reactor 500 may comprise a plurality of SMR process microchannels in thermal contact with a plurality of combustion channels. A combustion reaction may be conducted in the combustion channels to provide the heat displayed for the endothermic SMR reaction. In process operation 100E, a carbonaceous material enters the carbonator 110 through line 112 where it is combined with a carbonating agent that enters carbonator 110 through line 114. The carbonaceous material and the carbonating agent are heated and subjected to a reaction. gasification to form synthesis gas. Synthesis gas flows through line 116 to the microchannel reactor, 200 where it contacts a catalyst and reacts to form one or more hydrocarbons or one or more alcohols as discussed above. The product flows out of the microchannel reactor 200 through line 202. A waste gas comprising methane is separated from the product and flows from line 202 through line 208 to the microchannel reactor SMR 500. The remainder of the product (i.e. (product minus residual gas) flows out of the system through line 210. The residual gas along with steam flows through the SMR 500 microchannel reactor. The residual gas and steam are subjected to an SMR reaction and are converted to gas. of synthesis. The synthesis gas flows from the SMR 500 microchannel reactor through line 502 to the microchannel reactor 200 where it is combined with the synthesis gas flowing from the gasifier 110. The combined synthesis gas mixture flows into the microchannel reactor. 200 and is subjected to the reaction as described above. Process 100F shown in Fig. 7 is the same as process 100E shown in Fig. 6 except that carbon dioxide is separated from the synthesis gas flowing out of the gasifier 110 through line 116 as indicated by arrow 120. Low carbon dioxide synthesis (ie the synthesis gas minus carbon dioxide) flows through line 122 into the microchannel reactor 200 where it is combined with the synthesis gas from line 502. The combined synthesis is subjected to reaction in the microchannel reactor 200 to form one or more hydrocarbons or one or more alcohols as described above. Process 100G shown in Figure 8 is the same as process 100F shown in Figure 7 except that carbon dioxide that is separated from the synthesis gas that flows out of carbonator 110 through line 116 flows through line 120 to SMR 500 microchannel reactor where it is combined with the waste gas and reacts to form synthesis gas. This synthesis gas flows out of the SMR 500 microchannel reactor through line 502 to microchannel reactor 200. In microchannel reactor 200, the synthesis gas from line 502 is combined with the synthesis gas from line 502. 122 and is subjected to the reaction to form one or more hydrocarbons or one or more alcohols as discussed above. Process 100H shown in Fig. 8A is the same as process 100 shown in Fig. 1 except that the product flowing out of the microchannel reactor 200 through line 202 comprises a Fischer-Tropsch product. The Fischer-Tropsch product may comprise a mixture of liquid and gas. The gaseous Fischer-Tropsch product can be separated from the liquid Fischer-Tropsch product as indicated by arrow 203. The liquid Fischer-Tropsch product can then be subjected to a hydrocracking reaction in the hydrocracking microchannel reactor 700. Optionally, the Fischer liquid product -Tropsch can be separated into a light fraction and a heavy fraction into a separation unit or a distillation unit. The heavy fraction may be fed to the hydrocracking microchannel reactor 700. The light fraction may be taken as a finished product or processed separately. Alternatively, the light fraction may be introduced into the hydrocracking microchannel reactor 700 that is processing the heavy fraction. The light fraction may be hydrocracked in a separate hydrocracking microchannel reactor. The Fischer-Tropsch liquid product flowing from line 202 can enter the hydrocracking microchannel reactor 700 where it can be combined with a hydrogen feed stream. The hydrogen feed stream enters the hydrocracking microchannel reactor 700, as indicated by arrow 702. In the hydrocracking350channel microchannel reactor 700, the Fischer-Tropsch product and hydrogen contact a hydrocracking catalyst and react to form the desired hydrocracking product. The hydrocracked product flows out of hydrocracking microchannel reactor 700 as indicated by arrow 704. In an alternative embodiment, the liquid Fischer-Tropsch product may be separated into a light fraction and a heavy fraction, and then only the heavy fraction would be hydrocracked. in hydrocracking microchannel reactor 700. The hydrocracking process is exothermic. This reaction can be controlled using a heat exchange fluid that flows through the microchannel reactor 700 as indicated by arrows 706 and 708. However, the use of heat exchange fluid may be optional due to the fact that the hydrocracking reaction it can only be exothermic.

In an alternative embodiment, the hydrocracking reaction may be conducted in the same microchannel reactor used to conduct the Fischer-Tropsch reaction. In this embodiment, the microchannel reactor 200 used to conduct the Fischer-Tropsch reaction may be modified to include a hydrocracking reaction zone downstream of the Fischer-Tropsch reaction zone. Hydrogen feed would flow into the hydrocracking reaction zone. The microchannel reactor 200 can also be modified to allow removal of gaseous Fischer-Tropsch products and optionally light fractionated liquid Fischer-Tropsch products downstream of the Fischer-Tropsch reaction zone but upstream of the hydrocarbon reaction zone. The gasification step (A) of the inventive process involves converting the carbonaceous material into synthesis gas by reacting the carbonaceous material at a temperature of at least about 700 ° C with a gasification agent. The gasifying agent may comprise oxygen, air and / or vapor. The gasification step (A) may be conducted at a temperature of at least about 800 ° C, and in a mode at a temperature of at least about 900 ° C, and in a mode at a temperature of at least about 1000 ° C. and in one embodiment at a temperature of at least about 1100 ° C, and in one embodiment at a temperature of at least about 1200 ° C. The gasification step (A) may be conducted at a temperature in the range of approximately 7700 ° C to approximately 2500 ° C, and in a mode in the range of approximately 800 ° C to approximately 2200 ° C, and in a mode in the range of 900 ° C to about 2000 ° C, and in a mode in the range from about 1000 ° C to about 1800 ° C, and in a mode in the range from about 1100 ° C to about 1800 ° C, and in a mode in the range from approximately 1300 ° C to approximately 1500 ° C. The elevated temperatures used during step (A) distinguish it from biological processes such as anaerobic digestion that produces biogas.

While not wishing to be bound by theory, it is believed that during step (A) of the inventive process, the carbonaceous material may be subjected to the following processes: 1. A pyrolysis (or devolatilization) process may occur as the carbonaceous material warms up. Volatiles can be released and charcoal can be produced, resulting, for example, in losing up to approximately 70% by weight. The process may be dependent on the properties of the carbonaceous material. These properties can determine the structure and composition of char. 2. A combustion process may occur as volatile products and some charcoal react with oxygen to form carbon dioxide and carbon monoxide. This can provide heat for subsequent gasification reactions. 3. Reaction of char with carbon dioxide and steam to produce carbon monoxide and hydrogen. 4. A reversible gas phase water gas displacement reaction can achieve equilibrium in the gasifier temperatures. This can result in equilibrium carbon monoxide, vapor, carbon dioxide and hydrogen concentrations. C0 + H20 <-> C02 + H2 With these processes, a limited amount of oxygen can be introduced into the gasifier to allow some of the carbonaceous material. be burned to produce carbon monoxide and energy in a first reaction. The molar ratio of oxygen to carbon may be in the range of approximately 0.01: 1 to approximately 5: 1, and in a mode in the range of approximately 0.2: 1 to approximately 2: 1, and in a mode in the range of approximately 0.2: 1 to approximately 5: 1. approximately 0.5: 1 to approximately 1.5: 1, and in a mode in the range of approximately 0.5: 1 to approximately 1.2: 1, and in a mode of approximately 1: 1. This reaction can be used to trigger a second reaction that converts additional carbonaceous material into hydrogen and additional carbon monoxide. The gasification step (A) may be conducted in a countercurrent fixed bed gasifier, a co-current fixed bed gasifier, a fluidized bed gasifier, or an entrapped flow gasifier. The countercurrent fixed bed gasifier may comprise a fixed bed of carbonaceous material through which the gasification agent (e.g. steam, oxygen and / or air) flows in countercurrent configuration. Ash can be removed dry or as slag. Slag forming aerators may require a higher vapor and oxygen to carbon ratio to reach higher temperatures than the ash melting temperature. The carbonaceous material may require high mechanical strength and a non-mass forming composition so that it can form a permeable bed. Productivity for this type of carbonator can be relatively low. Thermal efficiency can be high as gas outlet temperature can be relatively low, tar and methane can be produced with this process. The co-current fixed bed gasifier is similar to the countercurrent type, except that the gasification agent flows in co-current configuration with the carbonaceous material. Heat may need to be added to the top of the bed by combustion of small amounts of carbonaceous material or external heat sources. Synthesis gas may leave the gasifier at a high temperature. Much of this heat can be transferred to the gasification agent added at the top of the bed to provide energy efficiency. Tars can pass through a warm charcoal bed in this setting. However, tar levels may be lower than with countercurrent.

In the fluidized bed gasifier, the carbonaceous material may be fluidized in the gasification agent. Ash can be removed dry or as heavy agglomerates that defulidize. The temperature may be relatively low in dry ash gasifiers and, as such, the carbonaceous material may be relatively highly reactive; Low grade coals may be particularly suitable. Agglomerating gasifiers may operate at slightly higher temperatures, and may be suitable for higher grade coals. The yield of carbonaceous material may be higher than for the fixed bed, but not as high as for the trapped flow gasifier. The conversion efficiency can be quite low due to the elutriation of carbonaceous material. Subsequent combustion or solids recycling can be used to increase conversion. Fluidized bed gasifiers may be useful for highly corrosive ash-forming carbonaceous materials that can damage the slag-forming gasifier walls.

In the trapped flow gasifier a dry pulverized solid carbonaceous material, an atomized liquid carbonaceous material, or a paste of carbonaceous material may be gasified with oxygen or co-flowing air. Gasification reactions can occur in a dense cloud of very fine particles. Most coals may be suitable for this type of gasifier due to high operating temperatures and because the coal particles can be well separated from each other. High temperatures and pressures may also mean that higher productivity can be obtained, however, the thermal efficiency may be somewhat lower since the gas may be cooled before it can be cleaned. High temperatures may also mean that tar and methane may not be present in the product synthesis gas; however, the oxygen requirement may be higher than for other types of gasified ones. Trapped flow gasifiers can remove much of the ash as slag since the operating temperature may be above the ash melting temperature. A smaller fraction of the ash can be produced as a very fine dry fly ash or as a black fly ash paste. Some carbonaceous materials, in particular certain types of biomass, may form slag that is corrosive to ceramic interior walls that may serve to protect the outer wall of the carbonator. However, some types of trapped bed aerators may not have an internal ceramic wall but may have an internal steam or water cooled wall covered with partially solidified slag. These types of gasifiers may not suffer from corrosive slag. Some carbonaceous materials may have ashes with very high ash melting temperatures. In this case limestome may be mixed with the fuel before gasification. The addition of limestone may be sufficient to lower melting temperatures. Particles of carbonaceous material may be smaller than for other types of gasifiers. This may mean that carbonaceous material can be sprayed, which may require more energy than for other types of gasifiers. The gasification step (A) may be conducted in a molten metal reactor. In the molten metal reactor, the carbonaceous material and vapor contact molten metal and react to form the synthesis gas. The molten metal may comprise a reactive metal (Me) that reacts with a first portion of the vapor entering the reactor according to the following equation: xMe + yH20 -> yH2 + Mex0y the carbonaceous material may react with a second portion of the vapor to form carbon monoxide and hydrogen. Reactive metal may have an oxygen affinity that is similar to oxygen affinity of hydrogen. The reactive metal may comprise one or more of the following metals or their alloys: germanium, iron, zinc, tungsten, molybdenum, indium, tin, cobalt or antimony. The reactive metal may be at least partially dissolved in a second metal or mixture of metals. The metal into which the reactive metal is dissolved may be referred to as diluent metal. The diluent metal may also be steam reactive, in which case it may be selected from the reactive metals disclosed above, provided that the diluent metal is less reactive than the reactive metal. The diluent metal may comprise one or more of nickel, copper, ruthenium, rhodium, palladium, silver, cadmium, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, selenium or tellurium. More than one diluent metal may be used in the molten metal mixture. In one embodiment, the reactive metal may comprise iron, and the diluent metal may comprise tin. Molten metal reactors that may be used to convert carbonaceous material into synthesis gas may include the molten metal reactors disclosed in US Patent 7,232,472 B2; 6,685,754B2; 6,682,714B2; and 6,663,681B2; which are incorporated herein by reference. The gasification step (A) may be conducted in a plasma based gasification system. With such a system, the carbonaceous material may be fed into a plasma converter which may comprise a sealed stainless steel container filled with nitrogen or ordinary air. An electric current (For example, an electric current of 650 volts) can be passed between two electrodes; This removes electrons from nitrogen or air and creates plasma. A constant flow of electricity through the plasma maintains an intense energy field powerful enough to disintegrate the carbonaceous material into its component elements. The by-products may comprise a glass-like substance which may be used as a raw material for high strength asphalt or household tiles, and synthesis gas. Synthesis gas may exit the plasma converter at an elevated temperature, for example approximately 1204 ° C. The synthesis gas can then be fed into a steam generating cooling system. This steam can be used to power the turbines that produce electricity, part of which can be used to power the plasma converter, while the rest can be used for the power or heating needs of the plant, or sold back to the utility. public services. The synthesis gas can then be advanced to microchannel reactor 200.

One or more of the Fischer-Tropsch (FT) 200 alcohol-forming microchannel reactors, or one or more of the SMR 500 microchannel reactors, or one or more of the 70 'hydrocracking microchannel reactors may be housed in container 220. Container 220 is of the construction illustrated in Figures 9 and 10. Referring to Figures 9 and 10, container 220 contains five Fischer-Tropsch 200 alcohol-forming microchannel reactors, or five SMR 500 microchannel reactors, or five 700 hydrocracking microchannel reactors. These are identified in the drawings as 200/500/700 microchannel reactors. These are identified in Figure 10 as alcohol-forming or Fischer-Tropsch microchannel reactors, SMR microchannel reactors, or 200/500 / 700-1, 200/500 / 7700-2, 200/500 / micro-channel reactors. 700-3, 200/500 / 700-4 and 200/500 / 700-5. Although five microchannel reactors are disclosed in the drawings, it will be understood that any desired number of Fischer-Tropsch alcohol-forming microchannel reactors, or SMR microchannel reactors, or hydrocracking microchannel reactors may be positioned in vessel 220. For example container 220 may contain from about 1 to about 1000 microchannel reactors 200, 500, or 700 and in a mode from 1 to about 750, and in a mode from about 1 to about 500, and in a mode from 1 to about 250 and in a mode of from 1 to about 200, and in a mode of from about 1 to about 50, and in a mode of from 1 to about 20 microchannel reactors 200, 500, or 700. Container 220 may be a pressurizable container. Container 220 includes inlets 224 and 228, and outlets 222 and 226.

When vessel 220 is used with the Fischer-Tropsch 200 or microchannel reactors, the inlet 224 is connected to a piping that is supplied for synthesis gas flow to the Fischer-Tropsch or microchannel process microchannels. on microchannel reactors 200. Input 228 is connected to a piping that is provided for heat exchange fluid flow (eg steam) for channel heat exchange on microchannel 200 reactors. Output 222 is connected to a tubing that provides product flow from the alcohol-forming or Fischer-Tropsch microchannels in microchannel reactors 200. Output 226 is connected to a tubing to provide heat exchange fluid flow out of the heat exchange in microchannel reactors 200.

When container 220 is used with the SMR 500 microchannel reactors, container 220 includes output 222 and inputs 224, 226, and 228. Input 224 is connected to a piping that is supplied for SMR feed flow (for example, gas FT and steam) to the SMR process microchannels in the SMR 500 microchannel reactors. Input 228 is connected to a pipeline that is supplied for fuel flow (eg natural gas to the combustion channels in the SMR 500 microchannel reactors). Output 222 is connected to a pipeline that provides the flow of synthesis gas from the SMR 500 microchannel reactors out of container 220. Input 226 is connected to a pipeline to provide oxygen flow or oxygen source. (for example, air) for stage addition channels in the SMR 500 microchannel reactors. Container 220 also includes an outlet (not shown in the drawings) that provides the flow of exhaust gas from the SMR 500 microchannel reactors.

When vessel 220 is used with hydrocracking microchannel reactors 700, inlet 224 is connected to a piping that is provided for Fischer-Tropsch product flow from line 202 for hydrocracking process microchannels in microchannel reactors 700. Container 220 also includes an inlet (not shown in the drawings) for hydrogen flow through a tubing into the microchannel reactor process microchannels 700. Inlet 228 may be connected to a tubing that is supplied for hydrogen flow. heat exchange channels for heat exchange channels in 700-channel reactors. Output 222 is connected to a pipeline that provides a flow of a hydrocracked Fischer-Tropsch product out of process microchannels in 700-channel reactors. Output 226 can be connected to a pipeline to provide heat exchange fluid flow out of the heat exchange channels in the micro reactors 700. The hydrocracking reaction involving the Fischer-Tropsch product may only be slightly exothermic, and as such, the use of heat exchange channels in the microchannel reactor 700 may not be necessary and can therefore be considered as optional. Microchannel reactor 700 may advantageously be used, with or without heat exchange channels, to hydrocharge the Fischer-Tropsch product due to the fact that when using microchannel reactor 700, increased mass transfer between the feed gas hydrogen and the Fischer-Tropsch product can be obtained. Container 220 may be constructed using any suitable material sufficient to operate under the pressures and temperatures required to operate the Fischer-Tropsch 200 microchannel reactors, SMR 500 microchannel reactors, or hydrocracking microchannel reactors 700. For example, housing 221 and heads 223 of container 220 may be constructed of cast steel. The flanges, couplings and pipes may be constructed of 316 stainless steel. The container 220 may have any desired diameter, for example from about 10 to about 1000 cm, and in an embodiment of about 50 to about 300 cm. The axial length of the container 220 may be of any desired value, for example from about 0.5 to about 50 meters, and in an embodiment from about 1 to about 20 meters.

The Fischer-Tropsch Microchannel Reactors 200 may comprise a plurality of Fischer-Tropsch Microchannel Process Microchannels and heat exchange channels stacked over or positioned side by side. The alcohol-forming or Fischer-Tropsch 200 microchannel reactors may be in the form of cubic blocks. Each of these cubic blocks may have a length, width and height, the length being in the range of about 10 to about 1000 cm, and in one embodiment in the range of about 20 to about 200 cm. The width may be in the range of about 10 to about 1000 cm, and in a mode in the range of about 20 to about 200 cm. The height may be in the range of about 10 to about 1000 cm, and in a mode in the range of about 20 to about 200 cm.

Microchannel reactors 200 as well as containers 220 may be small and compact enough to be easily transportable. As such, these reactors and containers along with other equipment used in the inventive process can be easily transported to remote locations such as military bases and used to convert carbonaceous waste products such as solid waste, biomass, etc. to synthetic fuels such as automotive fuel. , diesel fuel, aviation fuel and the like.

The Fischer-Tropsch 200 microchannel reactors may individually comprise a plurality of repeating units, each of which includes one or more Fischer-Tropsch alcohol formation process channels and one or more alcohol exchange channels. heat. Repeating units that may be used include repeating units 230, 230A, 230B and 230C illustrated in figures 11-14, respectively. The Fischer-Tropsch 200 alcohol-forming microchannel reactors may comprise from about 1 to about 1000 of repeating units 230, 230A, 230B or 230C, and in an embodiment of from about 10 to about 500 of such repeating units. The catalyst used in the 230-230D repeating units may be in any form including the various structured forms of catalyst described below. The repeating unit 230 is illustrated in FIG. 11. Referring to FIG. 11, the Fischer-Tropsch or alcohol forming process microchannel 232 is positioned adjacent to the heat exchange layer 234 which contains heat exchange channels 236. heat exchange channels 236 may be microchannel. A common wall 237 separates process microchannel 232 from heat exchange layer 234. A catalyst is positioned in reaction zone 240 of process microchannel 232. In one embodiment, the length of the exchange layer is up to approximately 200%. of the length of the reaction zone 240, and in one embodiment the length of the heat exchange layer 234 is approximately 50 to about 175% of the length of the reaction zone, and in one embodiment the length of the heat exchange layer 234 is approximately 75% to about 150% of the length of reaction zone 240. Reagent composition (i.e. synthesis gas) flows into reaction zone 240 in process microchannel 232 in the direction indicated by arrow 250, contacts catalyst in the reaction zone, and react to form the desired product. Product (i.e. one or more hydrocarbons or one or more alcohols) flows out of process microchannel 232 as indicated by arrow 252. Heat exchange fluid flows through heat exchange channels 236 in a direction that is cross-current with the reactant composition and product flow in process microchannel 232. Alcohol or Fischer-Tropsch reactions conducted in process microchannel 232 are exothermic and the heat exchange fluid provides cooling for the reaction.

Alternatively, the process microchannels and heat exchange channels may be aligned as provided in the repeating unit 230A. repeating unit 230A, which is illustrated in Fig. 12, is identical to repeating unit 230, shown in Fig. 11 except that heat exchange channels 236 are rotated 90 ° and heat exchange fluid flowing through The heat exchange channel 236 flows in a direction that may be countercurrent to the reactant and product flow in the process microchannel 232 or co-current to the reactant and product direction in the process microchannel 232.

Alternatively, the process microchannels and heat exchange channels may be aligned as provided in the repeating unit 230B. The repeating unit 230B is illustrated in Fig. 13. Referring to Fig. 13, process microchannel 232a is positioned adjacent to heat exchange layer 236. Heat exchange layer 235 contains a plurality of heat exchange channels 236 aligned in parallel with each other, each heat exchange channel 236 extending lengthwise at a right angle to the length direction of process microchannel 232a. Heat exchange layer 236 is shorter in length than process microchannel 232a. heat exchange layer 236 extends lengthwise from or near inlet 246 to reaction zone 240 of process microchannel 232a to a point 247 along the length of process microchannel 232a just prior to outlet 248 of process. reaction zone 240. In one embodiment, the length of the heat exchange layer 235 is up to approximately 90% of the length of the reaction zone 240, and in one embodiment the length of the heat exchange layer 235 is approximately 5 to 10%. approximately 90% of the length of reaction zone 240, and in one embodiment the length of the heat exchange layer 235 is from about 5 to about 50% of the length of reaction zone 240, and in one embodiment the length of the reaction layer 240. heat exchange 235 is approximately 50% to approximately 90% of the length of reaction zone 240. The width of process microchannel 232a is expanded or extended in the area downstream of the 247 end of the t layer. heat stroke 235.

Alternatively, the process microchannels and heat exchange channels may be aligned as provided in the repeating unit 230C. repeating unit 230C, which is illustrated in Fig. 14, is identical to repeating unit 230B, shown in Fig. 13 except that repeating unit 230C includes heat exchange layer 235a adjacent to process microchannel 232a on the side. opposite of the process microchannel 232a from the heat exchange layer 235. The heat exchange layer 235a contains a plurality of parallel heat exchange channels 235a that are equal to or similar in size and design to the heat exchange channels. 236 discussed above. The heat exchange layer 235a extends lengthwise from or near the inlet 246 of reaction zone 240 of process microchannel 232a to a point 249 along the length of process microchannel 232a just before end 247 of layer heat exchange layer 235. The length of the heat exchange layer 235a may be up to approximately 90% of the length of the heat exchange layer 235, and in one embodiment the length of the heat exchange layer 235a may be approximately 5 to approximately 90% of the length of the heat exchange layer 235, and in one embodiment the length of the heat exchange layer 235a may be from about 5 to about 50% of the length of the heat exchange layer 235, and in one embodiment The length of the heat exchange layer 235a may be from about 50% to approximately 90% of the length of the heat exchange layer 235. The width of the process microchannel 232a is expanded in the downstream areas. at the ends 247 and 249 of the heat exchange layers 235 and 235a, respectively.

Process microchannels 232 and 232a may have cross sections having any shape, for example, square, rectangle, circle, half circle, etc. The internal height of each process microchannel 232 and 232a may be considered to be the smallest of the internal dimensions perpendicular to the reactant and product flow direction through the process microchannel. Each of the process microchannels 232 and 232a may have an internal height of up to approximately 10 mm, and in an embodiment up to approximately 6 mm, and in an embodiment up to approximately 4 mm, and in an embodiment up to approximately 2 mm. In one embodiment, the height may be in the range of approximately 0.05 to approximately 10 mm, and in an embodiment approximately 0.05 to approximately 6 mm, and in an embodiment approximately 0.05 to approximately 4 mm, and in an embodiment. approximately 0.05 to approximately 2 mm. The width of each process microchannel 232 and 232a may be considered to be the other internal dimension perpendicular to the reactant and product flow direction through the process microchannel. The width of each process microchannel 232 and 232a may be of any size, for example up to approximately 3 meters, and in one embodiment approximately 0.01 to approximately 3 meters, and in one embodiment approximately 0.1 to approximately 3 meters. The length of each process microchannel 232 and 232a may be of any size, for example up to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 6 meters. , and in a mode of 0.2 to approximately 3 meters.

The heat exchange channels 236 may be microchannel or may have larger dimensions that would classify them as non-microchannel. Each of the heat exchange channels 236 may have a cross section having any shape, for example a square, rectangle, circle, semicircle, etc. the internal height of each heat exchange channel 236 may be considered to be the smallest of the internal dimensions perpendicular to the heat exchange fluid flow direction in the heat exchange channels. Each of the heat exchange channels 236 may have an internal height of up to approximately 2 mm, and in an embodiment in the range of approximately 0.05 to approximately 2 mm, and in an embodiment of approximately 0.05 to approximately 1.5 mm. The width of each of these channels, which would be the other internal dimension perpendicular to the direction of heat exchange fluid flow through the heat exchange channel, can be of any dimension, for example up to approximately 3 meters, and in one embodiment. from about 0.01 to about 3 meters, and in a mode about 0.1 to about 3 meters. The length of each of the heat exchange channels 236 may be of any size, for example, up to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 10 meters. 6 meters, and in a mode of 0.2 to approximately 3 meters. The number of repeating units 230-230C in microchannel reactor 200 may be a desired number, for example one, two, three, four, six, eight, ten, hundreds, thousands, tens of thousands, hundreds of thousands, millions , etc.

In the design and operation of an alcohol-forming or Fischer-Tropsch microchannel reactor it may be advantageous to provide a molded heat exchange profile along the length of the process microchannels to optimize the reaction. This can be accomplished by matching the local release of heat from the alcohol or Fischer-Tropsch reaction conducted in the process microchannels with heat removal or cooling provided by the heat exchange fluid in the heat exchange channels in the microchannel reactor. The extent of the Fischer-Tropsch formation reaction and the resulting heat release provided by the reaction may be higher in the front sections or upstream of the reaction zones in the process microchannels compared to the rear sections or downstream of the zones. reaction Consequently, the matched cooling requirements may be higher in the upstream section of the reaction zones compared to the downstream sections of the reaction zones. Molded heat exchange can be accomplished by providing more cooling channels or heat exchange, and consequently the flow of more cooling fluid or heat exchange, in thermal contact with the upstream sections of the reaction zones in the process microchannels in process. compared to the downstream sections of the reaction zones. This is shown in figures 13 and 14 where heat exchange layers 235 and 235a extend lengthwise from inlet 246 to reaction zone 240 along the length of process microchannels 230B and 230C to the points 247 and 249 shortly before exit 248 of reaction zone 240. Alternatively or additionally, a molded heat exchange profile may be provided by varying the heat exchange fluid flow rate in the heat exchange channels. In areas where additional heat exchange or cooling is desired, the heat exchange fluid flow rate may be increased compared to areas where less heat exchange or cooling is required. For example, a higher heat exchange fluid flow rate may be advantageous in the heat exchange channels in thermal contact with the upstream sections of the reaction zones in the process microchannels compared to the heat exchange channels in the process. thermal contact with the downstream sections of the reaction zones. Thus, with reference to Figure 11, for example, a higher flow rate in the heat exchange channels 236 near the input of the process microchannel 232 or reaction zone 240 may be used compared to the heat exchange channels. 236 near the outlet of the process microchannel 232 or reaction zone 240 where the flow rate may be lower. Heat transfer from process microchannels to heat exchange channels can be designed for optimum performance by selecting optimal heat exchange channel dimensions and / or heat exchange fluid flow rate by individual or groups. of heat exchange channels. Additional design alternatives for heat exchange shaping may be related to the selection and design of an alcohol-forming or Fischer-Tropsch catalyst (such as particle size, catalyst formulation, packaging density, use of a graduated catalyst, or other product). chemical or physical characteristics) at specific locations in the process microchannels. These design alternatives can impact both heat release from process microchannels and heat transfer to heat exchange fluid. Temperature differentials between process microchannels and heat exchange channels, which may provide the driving force for heat transfer, may be constant or may vary over the length of process microchannels.

The SMR 500 microchannel reactors may comprise a plurality of SMR process microchannels, combustion channels and stepped addition channels stacked on or positioned side by side. The SMR 500 microchannel reactors may have the shape of cubic blocks as illustrated in figures 9 and 10. Each of these cubic blocks may have a length, width and height, the length being in the range of about 10 to about 1000 cm, and in a between 50 and 200 cm. The width can be in the range of about 10 to about 1000 cm, and in a mode in the range of about 50 to about 200 cm. The height may be in the range of about 10 to about 1000 cm, and in a mode in the range of about 50 to about 200 cm.

The SMR 500 microchannel reactors may comprise a plurality of repeating units, each of which includes one or more SMR process microchannels, combustion channels and stage addition channels. Repeating units that may be used include repeating units 510, 510A, 510B, 510C and 510D illustrated in Figures 21-25, respectively. The SMR 500 microchannel reactors may comprise from about 1 to about 1000 of the repeating units 510, 510Α, 510 ou, 510C or 510D, and in an embodiment of from about 3 to about 750, and in an embodiment of from about 5 to about 500. , and in a mode of about 5 to about 250, and in a mode of about 10 to about 100 of such repeating units. The repeat unit 510 illustrated in Figure 21 includes process microchannel SMR 512 and heating section 520. Heating section 520 comprises combustion channel 530 and stage addition channels 540 and 540A. process microchannel 510 is U-shaped upside down and includes reaction zone 516 where an SMR catalyst (not shown in the drawing) is positioned. SMR feed (For example, FT waste gas in combination with steam) enters the SMR process microchannel 512 as indicated by arrow 514, flows through the SMR process microchannel, contacts the SMR catalyst in reaction zone 516, is subjected to a vapor methane reforming reaction with the result being the formation of synthesis gas comprising CO and H2. Synthesis gas flows out of the SMR process microchannel as indicated by arrow 518. Combustion channel 530 is an M-shaped combustion channel that includes reaction zones 534 where a combustion catalyst (not shown in the drawing) is setted up. The combustion channel 530 also includes opening sections 538 in its sidewalls to allow oxygen or oxygen source to flow from the 540 and 540A stage addition channels into the combustion channel 530. A fuel enters the combustion channel 530 as indicated by arrows 532 and flows into reaction zones 534. Oxygen or oxygen source enters stage addition channels 540 and 540A as indicated by arrows 542 and 542A and flows through opening sections 548 and inwardly. reaction zones 534 in combustion channels 530. The fuel is mixed with the oxygen or oxygen source, contacts the combustion catalyst, and undergoes a combustion reaction that generates heat and combustion discharge. The combustion discharge flows out of the combustion channel 530 as indicated by the arrows 536. The repeat unit 510A shown in Figure 22 is the same as the repeat unit 510 except that the process microchannel SMR 512 in the repeat unit 510A It is a straight-flow, straight-flow microchannel rather than an upside-down U-shaped microchannel. The repeat unit 510A shown in Fig. 23 is the same as the repeat unit 510A except that the repeat unit 510B includes two adjacent SMR process microchannels, namely SMR process microchannels 512 and 512A. SMR 512 process microchannel is adjacent to combustion channel 530. SMR process microchannel 512A is adjacent to SMR process microchannel 512 and in thermal contact with combustion channel 530. Repetition unit 510C shown in Figure 24 is the same. to repeat unit 510A shown in Fig. 22 except that combustion channel 530 shown in Fig. 24 is a straight stroke channel, rather than an M-shaped channel, and only a stage addition channel 540 is used. The repeat unit 510D shown in Figure 25 is the same as the repeat unit 510C shown in Figure 24 except that the SMR 512 process microchannel in the repeat unit 510D is an upside down U-shaped microchannel instead of of a microchannel of straight course. Microchannel reactor 700 may comprise a plurality of hydrocracking process microchannels and stacked heat exchange channels. However, as indicated above, heat exchange channels may not be required for the hydrocracking microchannel reactor 700, and thus the use of heat exchange channels may be considered as optional. Hydrocracking microchannel reactor 700 may be in the form of a cubic block as illustrated in FIGS. 9 and 10. The cubic block may have a length in the range of about 10 to about 1000 cm, and in one embodiment in the range of about 20 to about 200 cm. The cubic block may have a width in the range of about 10 to about 1000 cm, and in a mode in the range of about 20 to about 200 cm. The cubic block may have a height in the range of about 10 to about 1000 cm, and in a mode in the range of about 20 to about 200 cm. Fischer-Tropsch product, or at least the liquid or heavy liquid portion of Fischer-Tropsch product, and hydrogen may enter the hydrocracking process microchannels, and a hydrocracking product may flow out of the hydrocracking process microchannels. Heat exchange fluid, when used, can flow through the heat exchange channels. The microchannel reactor 700 may have a feed flow manifold or tubing to provide the flow of reactants into the process microchannels, a product footer or tubing to provide the product flow out of the process microchannels. When heat exchange channels are employed with the microchannel 700 heat exchanger, a heat exchange inlet pipe may be used to provide the heat exchange fluid flow into the heat exchange channels, and a Heat exchange outlet can be used to provide heat exchange fluid flow out of the heat exchange channels. Hydrocracking microchannel reactor 700 may contain one or more repeating units. Each repeating unit may contain one or more process microchannels and optionally one or more heat exchange channels. Each of the process microchannels may contain one or more reaction zones where the reactants react to form the desired product. A catalyst in solid form may be present in one or more reaction zones. The catalyst may comprise a homogeneous catalyst immobilized on a solid. In one embodiment, each process microchannel may be combined with one or more adjacent reagent flow channels to provide hydrogen stage addition into the process microchannel. The process microchannel and adjacent reagent flow channel may have a common wall with a plurality of openings in the common wall. These openings can be used to provide hydrogen flow from the adjacent reagent flow channel into the process microchannel. The feed flow collector may comprise one or more pipes for dispensing mixtures of reagents to the process microchannels. Alternatively, the feed flow collector may comprise separate pipelines for separately distributing the reagents to the process microchannels and adjacent reagent flow channels.

The heat exchange channels in the Fischer-Tropsch 200 alcohol-forming microchannel reactor, the combustion channels and stage addition channels in the SMR 500 microchannel reactor, and the adjacent reagent flow channels and Heat, when used, in the hydrocracking microchannel reactor 700 may be microchannels or may have dimensions that would characterize them as non-microchannels. For example, these channels may have internal heights or widths of up to approximately 50 mm, and in one embodiment up to approximately 25 mm, and in an embodiment up to approximately 15 mm. The Fischer-Tropsch alcohol-forming process microchannels, the SMR process microchannels, and the hydrocracking process microchannels are microchannels. Each of the microchannels may have a cross section having any shape, for example a square, rectangle, circle, semicircle, etc. each microchannel may have an internal height of up to approximately 10 mm, and in an embodiment up to approximately 5 mm, and in an embodiment up to approximately 2 mm, and in an embodiment up to approximately 2 mm. The height of each of these microchannels may be in the range of about 0.05 to about 10 mm, and in a mode of approximately 0.05 to about 5 mm, and in a mode of approximately 0.05 to about 2 mm, and in an embodiment about 0.05 to about 1.5 mm. The width of each of these microchannels may be of any size, for example, up to approximately 3 meters, and in an embodiment of approximately 0.01 to approximately 3 meters, and in an embodiment of approximately 0.1 to approximately 3 meters. The length of each microchannel may be of any size, for example up to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 10 meters, and in an embodiment of approximately 0.2 to approximately 6 meters, and in one embodiment. from 0.2 to about 3 meters.

The Fischer-Tropsch alcohol-forming process microchannels and heat exchange channels in the Fischer-Tropsch 200 microchannel reactor, the SMR process microchannels, combustion channels and stage addition channels in the Fischer-Tropsch 200 reactor. SMR 500 microchannels, and the hydrocracking process microchannels, adjacent reagent flow channels, and heat exchange channels, when used, in the hydrocracking microchannel reactor 700, may have rectangular cross sections and be aligned in vertically oriented planes side by side. side or horizontally oriented stacked planes. These planes can be tilted at an inclined angle from the horizontal. These settings may be referred to as parallel card configurations. These channels can be arranged in compact modularized units for augmentation. The Fischer-Tropsch 200 Microchannel Reactor, SMR 500 Microchannel Reactor, and Hydrocracking Microchannel 700 can be made of any material that provides sufficient strength, dimensional stability, and heat transfer characteristics to allow process operation. wanted. These materials may include aluminum; titanium; nickel; platinum; rhodium; copper; chrome; alloys of any of the above metals; brass; steel (eg stainless steel); quartz; silicon or a combination of two or more thereof. Each microchannel reactor may be constructed of stainless steel with one or more aluminum or copper waveforms being used to form the channels. The Fischer-Tropsch 200 Microchannel Reactor, SMR 500 Microchannel Reactor, and Hydrocracking Microchannel 700 can be fabricated using known techniques including electrode discharge machining, conventional machining, laser cutting, photochemical machining, electrochemical machining, molding, water jetting, stamping, etching (eg chemical, photochemical or plasma etching) and combinations thereof. The Fischer-Tropsch 200 microchannel reactor, the SMR 500 microchannel reactor and the hydrocracking microchannel 700 may be constructed by forming wedges with removed portions that allow flow to pass through. A stack of wedges may be assembled by diffusion bonding, laser welding, diffusion welding, and similar methods to form an integrated device. Microchannel reactors can be assembled using a combination of wedges or blades and partial sheets or strips. In this method, the channels or voids can be formed by mounting strips or partial sheets to reduce the amount of material required. The Fischer-Tropsch 200 microchannel reactor, the SMR 500 microchannel reactor and the hydrocracking microchannel 700 may be constructed using waveforms in the form of right angle corrugated inserts. These right angle corrugated sheets can have rounded edges instead of sharp edges. These inserts can be nested between wedges or opposite flat sheets. In this way the microchannels can be defined on three sides by the corrugated insert and on the fourth side by one of the flat sheets. Process microchannels as well as heat exchange channels can be formed in this way. Microchannel reactors made using waveforms are disclosed in WO 2008/030467, which is incorporated herein by reference.

Fischer-Tropsch alcohol-forming process microchannels, SMR process microchannels and / or combustion channels, and hydrocracking process microchannels may contain one or more surface characteristics in the form of depressions in and / or projections from one or more interior walls of the process microchannels. Examples are shown in Figures 26 and 27. The heat exchange channels in the Fischer-Tropsch 200 alcohol-forming microchannel reactor and, when used in the hydrocracking microchannel reactor 700, as well as the adjacent reagent flow channels in hydrocracking microchannel reactor 700, they may also contain such surface characteristics. Surface features can be used to disrupt the flow of fluid flowing in the channels. These flow breaks may increase mixing and / or heat transfer. Surface features may take the form of decorated surfaces. The Fischer-Tropsch, SMR and / or hydrocracking microchannel reactors may be made by laminating a plurality of wedges together. One or both of the main wedge surfaces may contain surface features. Alternatively, the Fischer-Tropsch, SMR and / or hydrocracking microchannel reactors may be assembled using some sheets or wedges and some strips, or partial sheets to reduce the total amount of metal required to construct the device. A wedge containing surface features may be paired (on opposite sides of a microchannel) with another wedge containing surface features. Pairing can create better mixing or increased heat transfer compared to channels with surface characteristics or just a main surface. The decoration may comprise diagonal recesses that are arranged substantially over the full width of a microchannel surface. The decorated surface feature area of a wall may occupy part or all of the length of a microchannel surface. Surface characteristics may be positioned at least about 10%, and in at least about 20% mode, and in at least about 50% mode and at least about 80% of the length of a channel surface. Each diagonal recess may comprise one or more angles with respect to the flow direction. Successive recessed surface features may comprise similar or alternating angles to other recessed surface features.

In embodiments where surface features may be positioned on or on more than one microchannel wall, surface features on or on one wall may have the same (or similar) pattern as found on a second wall, but rotated around the line. center of the main channel medium volume flow direction. In embodiments where the surface features may be on or on opposite walls, the surface features on or on a wall may be approximately mirror images of the features on the opposite wall. In a mode where surface features are on or on more than one wall, the surface features on or on one wall may be of the same (or similar) pattern as found on a second wall, but rotated about a geometric axis that is orthogonal to the main channel medium volume flow direction. In other words, the surface characteristics can be rotated 180 degrees relative to the main channel mid-volume flow direction and rotated around the center line of the main channel mid-volume flow. Surface features on or on opposite or adjacent walls may or may not be directly aligned with each other, but may be repeated continuously along the wall for at least part of the length of the wall. Surface features can be positioned on three or more interior surfaces of a channel. For channel geometries with three or less sides, such as triangular, oval, elliptical, circular and the like, the surface features may cover from approximately 20% to approximately 100% of the microchannel perimeter.

A decorated surface may comprise multiple patterns stacked on top of each other. One pattern or set of holes may be placed adjacent to a heat transfer wall and a second pattern, such as a diagonal set of surface features may be stacked on top and adjacent to an open channel for flow. A sheet adjacent to an open gap may be decorated through the thickness of the sheet such that flow may pass through the sheet into an underlying pattern. Flow may occur as a result of advection or diffusion. As an example, a first sheet with a set of straight holes may be placed over a heat transfer wall, and a second sheet with a set of straight diagonal slots may be positioned on the first sheet. This can create more surface area to adhere to a catalyst. The pattern may be repeated at least in altered wall of the process microchannel. Patterns can be off-centered on opposite walls. The innermost decorated surfaces (those surfaces bordering a flow channel) may contain a pattern as a diagonal set. Diagonal assemblies can be oriented either "with the flow direction or one side oriented with the flow direction and the opposite side oriented" against "the flow direction. By varying surface characteristics on opposite walls, different flow fields and degrees Vorticity can be created in the fluid that shifts down from the center and open backlash.

Surface features can be oriented at angles to the direction of flow through the channels. Surface characteristics may be aligned at an angle from about 1 ° to about 89 °, and in an embodiment from about 30 ° to about 75 °, relative to the flow direction. The orientation angle may be an oblique angle. Tilted surface features can be aligned in the flow direction or against the flow direction. Fluid flow in contact with surface characteristics may force some fluid into depressions in surface characteristics, while other fluids may flow above surface characteristics. The flow within the surface characteristics may conform to the surface characteristic and is at an angle to the direction of the volume flow in the channel. As fluid exits the surface characteristics it can exert momentum in the x and y direction for an x, y, z coordinate system where the volume flow is in the z direction. This may result in agitation or rotation of the fluid flow. This pattern may be useful for blending.

Two or more surface feature regions in the process microchannels may be serially arranged such that fluid mixing may be performed using a first surface feature region, followed by at least a second surface feature region where a Different flow pattern can be used.

Surface features can have two or more layers stacked together or interlaced in a three-dimensional pattern. The pattern in each discrete layer can be the same or different. The flow can rotate or advection on each layer or only on one layer. Sub-layers, which may not be adjacent to the channel volume flow path, may be used to create additional surface area. The flow may rotate at the first level of surface characteristics and diffuse molecularly into the second or more sublayers to promote reaction. Three-dimensional surface features can be made through metal casting, photochemical machining, laser cutting, cauterization, ablation or other processes where variable patterns can be broken into discrete planes as if stacked on top of each other. Three-dimensional surface features may be provided adjacent to the volume flow path in the microchannel where surface features have different depths, shapes, and / or locations accompanied by sub-features with varying depth, shape, and / or pattern patterns.

An example of a three-dimensional surface feature structure may comprise recessed oblique angles or boundaries at the interface adjacent to the microchannel volume flow path. Below the boundaries may be a series of three-dimensional structures that connect to surface features adjacent to the volume flow path but are made of separate shape structures, depths and / or locations. It may be additionally advantageous to provide sublayer passages that do not fall directly under an open surface feature that is adjacent to the volume flow path within the microchannel but instead connects via one or more tortuous two-dimensional or three-dimensional passages. Such an approach may be advantageous for creating molded residence time distributions in the microchannels, where it may be desirable to have a wider versus narrower residence time distribution. The length and width of a surface feature may be defined in the same way as the length and width of a channel. Depth can be the distance that the surface feature sinks in or rises above the microchannel surface. The depth of the surface features may correspond to the direction of stacking a stacked and bonded microchannel device with surface features formed on or on the sheet surfaces. Dimensions for surface features may refer to the maximum dimension of a surface feature; For example, the depth of a rounded notch may refer to the maximum depth, that is, the depth at the bottom of the notch.

Surface features may have depths that are up to about 5 mm, and in a mode up to about 2 mm, and in a mode in the range from about 0.01 to about 5 mm, and in a mode in the range of about 0.01 approximately 2 mm, and in a mode in the range of approximately 0.01 mm to approximately 1 mm. The width of the surface features may be sufficient to almost cover the width of the microchannel (eg, herringbone designs) but in one embodiment (such as padding features) it may cover approximately 60% or less of the width of the microchannel, and in a mode of about 50% or less, and in a mode of about 40% or less, and in a mode of about 0.1% to about 60% of the microchannel width, and in a mode of approximately 0.1%. approximately 50% of the microchannel width, and in a mode of approximately 0.1% to approximately 40% of the microchannel width. The width of the surface characteristics may be in the range of approximately 0.05 mm to approximately 100 cm, and in a mode in the range of approximately 0.5 mm to approximately 5 cm, and in a mode in the range of approximately 1 to approximately 2 cm. cm. Multiple surface features or surface feature regions may be included in a channel, including surface features that lower at different depths in one or more microchannel walls. The recess spacing may be in the range of from about 0.01 mm to about 10 mm, and in an embodiment in the range of from about 0.1 to about 1 mm. Surface features may be present over the entire length of a microchannel or in portions or regions of the channel. The portion or region having surface characteristics may be intermittent to promote desired unitary operation or mixing (e.g., separation, cooling, etc.) in molded zones. For example, a one-centimeter section of a channel may have a tightly spaced set of surface features, followed by four inches of a flat channel without surface features, followed by a two-inch section of loosely spaced surface features. The term "loosely spaced surface features" may be used to refer to surface features with a step or feature-to-feature distance that is more than approximately five times the width of the surface feature.

Surface features may be positioned in one or more surface feature regions that extend substantially over the entire axial length of a channel. In one embodiment, a channel may have surface characteristics extending about about 50% or less of its axial length, and in one embodiment about about 20% or less of its axial length. In one mode, surface characteristics may extend from about 10% to about 100% of the axial length of the channel, and in a mode of about 20% to about 90% and in a mode of about 30% to about 80% and a modality from about 40% to about 60% of the axial length of a channel.

Each surface feature leg may be at an oblique angle to the volume flow direction. The characteristic span length or span may be defined as being perpendicular to the characteristic orientation. As an example, a surface feature may be a diagonal depression at a 45 degree angle to an orthogonal plane at the average volume flow direction in the main channel with a 0.38 mm aperture or span or span length. and a feature stroke length of 5.6 mm. The stroke length may be the distance from one end to the other end of the surface feature in the longest direction, while the span or length of the feature may be in the shortest (non-depth) direction. Surface feature depth can be the distance away from the main channel. For surface characteristics with a non-uniform width (span), the span may be the average span over the stroke length.

A surface feature may comprise a recess or protrusion based on the projected area at the base of the surface feature or top of the surface feature. If the area at the top of the surface feature is equal to or exceeds the area at the base of the surface feature, then the surface feature may be considered to be lowered. If the area at the base of the surface feature exceeds the area at the top of the surface feature then it may be considered to be projected. For this description, the surface features may be described as lowered although it should be understood that by changing the aspect ratio of the surface feature may alternatively be defined as protrusion. For a process microchannel defined by walls that intersect only the tops of surface features, especially for a flat channel, all surface features can be defined as recessed and it should be understood that a similar channel could be created by protruding surface features. from the base of a channel with a cross section including the base of surface features.

Fischer-Tropsch alcohol-forming process microchannels, SMR process microchannels and / or combustion channels, and / or hydrocracking process microchannels may be at least about 20% and in one embodiment at least about 35% and in at least about 50%, and at least about 70% and at least about 90% of the inner surface of the channels (measured in cross-section perpendicular to the length; that is, perpendicular to the direction of liquid flow through which contains surface characteristics. Surface features may cover a continuous stretch of at least about 1 cm, and in a mode at least about 5 cm. In the case of an enclosed channel, the percentage of surface feature coverage may be the portion of a surface-covered cross section compared to an enclosed channel extending uniformly from the base or top of the surface feature or a constant value. intermediate. The latter may be a flat channel. For example, if a channel had decorated upper and lower surfaces that are individually 0.9 cm wide (wide) and unrecorded side walls that are 0.1 cm high, then 90% of the channel surface would contain surface characteristics.

Alcohol-forming or Fischer-Tropsch microchannels, SMR process microchannels, and / or hydrocracking process microchannels may be enclosed on all sides, and in one embodiment the channels may have a rectangular or generally square cross-section ( In case of rectangular channel, surface feature decoration can be positioned on two main faces). For a generally square or rectangular channel, the channels can be enclosed only on two or three sides and only the two or three walled sides can be used in the above described percentage of surface feature. Surface features can be positioned in cylindrical channels with constant or variable cross section in the axial direction.

Each of the surface feature patterns can be repeated along one channel face, with variable or regular spacing between surface features in the channel volume flow direction. Some modalities may have only a single leg for each surface feature, while other modalities may have multiple legs (two, three or more). For a wide channel, multiple surface features or columns of repeated surface features may be placed adjacent to each other across the width of the channel. For each of the surface feature patterns, the feature depth, width, span, and spacing may be variable or constant as the pattern is repeated along the volume flow direction in the main channel. In addition, surface feature geometries having an apex connecting two legs at different angles may have alternate embodiments in which the surface feature legs may not be connected at the apex. The Fischer-Tropsch catalyst may comprise any Fischer-Tropsch catalyst. The Fischer-Tropsch catalyst may comprise at least one catalytically active metal or oxide thereof. In one embodiment, the Fischer-Tropsch catalyst may further comprise a catalyst support. In one embodiment, the Fischer-Tropsch catalyst may further comprise at least one promoter. The catalytically active metal may comprise Co, Fe, Ni, Ru, Re, Os or a combination of two or more thereof. The support material may comprise alumina, zirconia, silica, aluminum fluoride, fluorinated alumina, bentonite, ceria, zinc oxide, silica alumina, silicon carbide, a molecular sieve, or a combination of two or more thereof. The support material may comprise a refractory oxide. The promoter may comprise a Group IA, IIA, IIIB or IVB metal or oxide thereof, a lanthanide metal or metal oxide, or an actinide metal or metal oxide. In one embodiment, the promoter is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th, or an oxide. thereof, or a mixture of two or more thereof. Examples of catalysts that may be used include those disclosed in US patents 4,585,798; 5,036,032; 5,733,839; 6,075,062; 6,136,868; 6,262,131B1; 6,353,035B2; 6,368,997B2; 6,476,085B2; 6,451,864B1; 6,490,880B1; 6,537,945B2; 6,558,634B1; and US Patent Publications 2002/002885 3Al; 2002 / 0188031A1; and 2003 / 0105171A1; such patents and patent publications being incorporated herein by reference for their disclosures of Fischer-Tropsch catalysts and methods for preparing such catalysts. The Fischer-Tropsch catalyst may comprise Co, and optionally a cocatalyst and / or promoter, supported on a support wherein the Co charge is at least about 5 wt%, and in an embodiment at least about 10 wt%. , and in a mode at least about 15 wt%, and in a mode at least about 20 wt%, and in a mode at least about 25 wt%, and in a mode at least about 28 wt%, and in a mode at least about 30 wt%, and in a mode at least about 32 wt%, and in a mode at least about 35 wt%, and in a mode at least about 40 wt%. In one embodiment, the Co charge may be from about 5 to about 50% by weight, and in a mode from about 10 to about 50% by weight, and in a mode from about 15 to about 50% by weight, and in a mode. about 20 to about 50% by weight, and in a mode about 25 to about 50% by weight, and in a mode about 28 to about 50% by weight and in a mode about 30 to about 50% by weight, and a approximately 32 to about 50% by weight. The metal dispersion to the catalytically active metal (i.e. Co and optionally cocatalyst and / or promoter) of the catalyst may range from approximately 1 to approximately 30%, and in an embodiment of from about 2 to approximately 20%, and in a mode about 3 to about 20%. The cocatalyst may be Fe, Ni, Ru, Re, Os, or an oxide thereof, or a mixture of two or more thereof. The promoter may be a Group IA, IIA, IIIB or IVB metal or oxide thereof, a lanthanide metal or metal oxide, or an actinide metal or metal oxide. In one embodiment, the promoter is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th, or an oxide. thereof, or a mixture of two or more thereof. The cocatalyst may be employed at a concentration of up to approximately 10% by weight based on the total weight of the catalyst (i.e. the weight of the catalyst, cocatalyst, promoter and support) and in an embodiment of from about 0.1 to approximately 5% by weight. The promoter may be employed in a concentration of up to approximately 10 wt% based on the total weight of the catalyst, and in an embodiment of approximately 0.1 to approximately 5 wt%. The Fischer-Tropsch catalyst may comprise alumina supported Co; the Co charge being at least about 25 wt%, and in a mode at least about 28 wt%, and in a mode at least about 30 wt%, and in a mode at least about 32 wt%, and Co dispersion is at least about 3% and in a mode at least about 5%, and in a mode at least about 7%. The Fischer-Tropsch catalyst may comprise a composition represented by the formula CoM1aM2bOx wherein: M1 is Fe, Ni, Ru, Re, Os or a mixture thereof, and in one embodiment M1 is Ru or Re or a mixture thereof; M2 is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th, or a mixture of two or more of the same; a is a number in the range from zero to about 0.5, and in a mode from zero to about 0.2; b is a number in the range from zero to about 0.5, and in a mode from zero to about 0.1; and x is the number of oxygen required to meet the valence requirements of the elements present. Fischer-Tropsch catalyst can be made using multiple impregnation steps where intercalcination steps are conducted between each impregnation step. Use of such a procedure, at least in one embodiment, allows the formation of catalysts with catalytic metal loading levels and optionally promoters that are higher than with procedures where such interleaving steps are not employed. In one embodiment, a catalytic metal (e.g. Co) and optionally cocatalyst (e.g. Re or Ru) and / or promoter are loaded onto a support (e.g. AI2O3) using the following sequence of steps: (A ) impregnating the support with a composition comprising a catalytic metal and optionally a cocatalyst and / or promoter to provide an intermediate catalytic product; (B) calcining the intermediate catalytic product formed in step (A); (C) impregnating the calcined intermediate formed in (B) with another composition comprising a catalytic metal and optionally a cocatalyst and / or promoter to provide another intermediate catalytic product; and (D) calcining the other intermediate catalytic product formed in step (C) to provide the desired catalytic product. The catalytic metal and optional cocatalyst and / or promoter may be impregnated into the support using an incipient moisture impregnation process. Steps (C) and (D) may be repeated one or more additional times until the desired charge of catalytic metal, and optional cocatalyst and / or promoter, is obtained. The composition comprising the catalytic metal may be a metal nitrate solution, for example a cobalt nitrate solution. The process may be continued until the catalytic metal (i.e. Co) achieves a charge level of approximately 20 wt% or more, and in a mode of approximately 25 wt% or more, and in a mode of approximately 2 wt%. 8 wt.% Or more, and in a mode approximately 30 wt.% Or more, and in a mode approximately 32 wt.% Or more, and in a mode approximately 35 wt.% Or more, and in a mode approximately 37% by weight or more, and in one embodiment approximately 40% by weight or more. Each of the calcination steps may comprise heating the catalyst to a temperature in the range of from about 100 ° C to about 500 ° C and in a mode of about 100 ° C to about 400 ° C, and in a mode of about 250 to about 350 ° C. for about 0.5 to about 100 hours, and in a mode about 0.5 to about 24 hours, and in a mode about 2 about 3 hours. The temperature may be inclined to the calcining temperature at a rate of approximately 1-20 ° C / min. The calcination steps may be preceded by drying steps where the catalyst is dried at a temperature of about 75 to about 200 ° C, and in a mode of about 75 ° C to about 150 ° C, for about 0.5 to about 100 ° C. hours and in a mode about 0.5 to about 24 hours. In one embodiment, the catalyst may be dried for approximately 12 hours at approximately 90 ° C and then at approximately 110-120 ° C for approximately 1 - 1.5 hours, the temperature being raised from 90 ° C to 110-120 ° C at a rate of approximately 0.5 - 1 ° C / min.

The Fischer-Tropsch catalyst may comprise a mixed metal, metal oxide or metal oxide. The metal may be cobalt, iron, ruthenium or a mixture of two or more thereof. The catalyst may comprise Co, or a carbide or oxide thereof. Such catalysts may also comprise one or more alkali metals, alkaline earth metals, transition metals, rare earth metals and / or lanthanides. Such a catalyst may be supported, in which case useful support materials may include metal oxides, for example alumina, titania, zirconia, as well as silica, mesoporous materials, zeolites, refractory metals, or combinations of two or more thereof. The support may be modified by the addition of small amounts of one or more transition metal oxides. The catalyst may be any of the Fischer-Tropsch catalysts disclosed in WO2008 / 104793 A2 which is incorporated herein by reference. The Fischer-Tropsch catalyst may comprise cobalt in an amount of up to about 60% by weight, and in an embodiment of from about 10% to about 60% by weight, and in an embodiment of from about 60% to about 60% by weight, and in an embodiment of from approximately 30% to approximately 60% by weight, and in an embodiment of approximately 35% to approximately 60% by weight, and in an embodiment of approximately 35% to approximately 50% by weight. Such catalysts may comprise cobalt and a support. The Fischer-Tropsch catalyst may comprise cobalt and a support, such catalyst may be activated using the process disclosed in US Patent 7,183,329 B2, which is incorporated herein by reference. Such a process comprises activating a catalyst precursor comprising a cobalt compound and a support with a gas comprising at least about 5 mol% of a hydrocarbon. The term "catalyst" may be used herein to cover both the catalyst in active form and the catalyst in precursor form as it may be subject to change in the reaction environment. The term "catalyst precursor" should be interpreted broadly, covering not only a freshly prepared catalyst precursor or a catalyst precursor that is unreduced or not used in a catalyzing reaction, but also any precursor that can be used as catalyst after activation. as a catalyst that was already used in a catalyzing reaction. Similarly the term "activation" should be understood to include not only activation as an unused or unused catalyst precursor but also activating a used or reduced catalyst. Therefore, the term includes within its scope any activation, including regeneration of a used catalyst. The Fischer-Tropsch catalyst may be prepared by activating a catalyst precursor with a hydrocarbon. The catalyst precursor may contain a cobalt compound and a support, the support may be any support that is capable of containing the catalyst in the desired reaction. The support may be an inert support, or it may be an active support. Examples of supports that may be used include alumina, modified alumina, spinel oxides, silica, modified silica, magnesium, titania, zirconia, a zeolite, beta-aluminate and carbon forms. The alumina or modified alumina may be, for example, alpha-alumina, beta-alumina or gamma-alumina. Beta-alumina and spinel oxides such as barium hexaaluminate may be advantageous because of their stability. The carbon may be in the form of active carbon or carbon nanotubes. A zeolite may be used. The support may contain pores or channels.

Any cobalt compound may be used with the catalyst precursor. The cobalt compound may be in the form of a salt, for example an aqueous soluble salt, or an oxide. Examples of cobalt salts that may be used may include cobalt nitrate, acetate, benzoate, oxalate or acetyl acetonate. It may be desirable to avoid the use of a cobalt halide as the halide may interfere with the support, an example of a cobalt oxide that may be used is Co304. One or more cobalt salts and / or oxides may be used. The catalyst precursor may be formed using any known procedure. The catalyst precursor may be added to the solution support using a solvent such as water or an organic solvent such as alcohol, the alcohol may contain from 1 to about 4 carbon atoms. These may include methanol and ethanol. The solvent may subsequently be removed. The solvent may be removed by drying at room temperature or above room temperature, for example from approximately 50 ° C to approximately 250 ° C for approximately 1 to approximately 24 hours. A combination of drying steps may be used. The supported catalyst precursor may be dried at room temperature for approximately 2 to 10 hours, and subsequently dried at an elevated temperature, for example from approximately 100 ° C to approximately 200 ° C, and in a mode of approximately 120 ° C for approximately 2 to 10 hours. about 8 hours. The solution comprising the catalyst precursor may further comprise additional components if desired. For example, it may also comprise a promoter or modifier. Promoters may include alkaline earth salts such as magnesium, calcium, barium and / or strontium nitrate. Promoters may also include alkali metal, alkaline earth metal or transition metal oxides that are derivable from their aqueous soluble compounds, such as their salts, for example, LINO3, KNO3, RbNO3, Ba (NO3) 2, Mg (NO3) 2r Ca (NO03) 2, Sr (NO03) 2, Zr (NO03) 2.xH20, Ce (NO03) 3.xH20 and U0 (NO03) 2 · Promoters may be loaded onto the support in any way, for example, by impregnation, especially sequential impregnation or co-impregnation with the cobalt compound.

Modifiers may include rare earth modifiers such as rare earth oxides or salts or transition metal, for example cerium and / or lanthanum acetate or nitrate or d-block transition metal oxides such as Mn, W, Nb and Vn. Modifiers may be derived from their aqueous soluble compounds as salts, and may be impregnated on the catalyst support, followed by calcination in air at a temperature in the range of approximately 300 ° C to approximately 1000 ° C for approximately 1 to approximately 24 hours in air. . Promoters and modifiers may be used individually or in a combination of two or more thereof. The supported catalyst precursor may be formed using a sol gel method. This method is described, for example, in Gonzalez et al., Catalysis Today, 35 (1997), 293-317 and J. Livage, Catalysis Today, 41 (1998), 19. Initial "freezing", an alkoxide or alcohol and a metal precursor may be hydrolyzed and condensed to a gel, for example in the presence of water. A cobalt compound may then be added in a subsequent "post-freezing" step, the gel may then be dried and calcined. The supported catalyst precursor may comprise from about 0.05 to about 30 wt% cobalt, and in an embodiment from about 0.5 to about 15 wt% cobalt. The supported catalyst precursor may comprise from about 0.5 to about 50% by weight of a cobalt compound; from 0 to about 10% by weight of promoter; and from 0 to about 20% by weight of modifier, or from about 0.01 to about 5% by weight of modifier; based on the total weight of the supported catalyst precursor. The supported catalyst precursor may comprise from about 5 to about 40 wt% of a cobalt compound, from 0 to about 3 wt% of promoter and from 0 to about 3 wt% of modifier. The supported catalyst precursor may be activated with a gas comprising a hydrocarbon. The hydrocarbon may be any hydrocarbon. It may be saturated or unsaturated, for example, containing from 1, 2, or 3 or more double and / or triple bonds. It can be linear, cyclic or branched. The hydrocarbon may also be aliphatic or aryl, or contains both aliphatic and aryl groups. The hydrocarbon may be a saturated or unsaturated hydrocarbon containing up to approximately 5 carbon atoms, and in an embodiment up to approximately 4 carbon atoms. The hydrocarbon may comprise methane, ethane, acetylene, propane, propene, butane or a mixture of two or more thereof. The activating gas may comprise at least about 5 mol% of the hydrocarbon, and in one embodiment at least about 10 mol% and in one embodiment at least about 20 mol%, and in one embodiment at least about 40 mol%. The gas comprising the hydrocarbon may comprise only the hydrocarbon or may further comprise up to about 10 mol%, and in an embodiment up to about 20 mol%, and in an embodiment up to about 40 mol% of an inert gas such as nitrogen and / or argon. It may also comprise a reactive component as another component which may also activate the catalyst precursor. For example, the gas may also comprise hydrogen. The gas may comprise methane and / or ethane in combination with hydrogen. If hydrogen is used, any hydrocarbon to hydrogen ratio may be used, for example, the ratio may be in the range of approximately 0.04: 1 or 0.05: 1 to approximately 100: 1 on a molar basis, or approximately 0.1: 1 or approximately 0.5: 1 to approximately 10: 1. Activation can be accomplished by placing the supported catalyst precursor in an atmosphere of the activation gas. The activation gas may be passed over the supported catalyst precursor. The activation temperature may be approximately 300 ° C or higher, for example from approximately 400 ° C to approximately 1000 ° C, or from approximately 400 ° C to approximately 800 ° C. The activation duration may be at least about 30 minutes, and in a mode at least about 1 hour, for example, from about 1 to about 20 hours, and in a mode of about 2 to about 5 hours. The activation temperature may vary depending on the nature of the catalyst and / or hydrocarbon precursor. Atmospheric pressure may be used for the activation step, although low or high pressure may also be used. The catalyst precursor may be activated in the reaction vessel in which it is intended to perform the reaction using the activated catalyst, or may be activated in a different vessel. The activated catalyst may undergo substantial oxidation when exposed to air. To stabilize the catalyst it can be treated in an atmosphere containing a small amount of oxygen, for example approximately 1% oxygen in an inert gas such as nitrogen or argon. The catalyst may be left in the activation reactor while bleeding in a small amount of oxygen. Thus, for example, the activated catalyst may be pacified for treatment in a reduced oxygen atmosphere, for example comprising less than approximately 20 mol% oxygen, or less than approximately 10 mol% oxygen, or less than approximately 5 mol%. of oxygen, or less than about 2 mol% oxygen for at least about 30 minutes, or at least about 1 hour. Fischer-Tropsch catalyst can be prepared using the process disclosed in US Patent No. 7,304,012 B2 which is incorporated herein by reference. Such a process involves preparing a supported catalyst or carbon-containing catalyst precursor. The process may comprise the steps of: (a) preparing a liquid mixture of (i) at least one catalyst support or catalyst support precursor; (ii) at least one metal-containing compound, wherein the metal is selected from V, Cr, Mn, Fe, Co, Ni, Cu, Mo and W, and (iii) at least one polar organic compound that acts as a solvent. for the metal containing compound, the liquid mixture comprising from 0 to about 20% by weight of water based on the total weight of the mixture; (b) convert the mixture to a paste or solid residue; and (c) burning the residue in an oxygen-containing atmosphere to at least partially convert the organic compound to carbon and form the supported catalyst or catalyst precursor.

In step (a), a liquid mixture may be prepared from at least three components: (i) a catalyst support or a catalyst support precursor; (ii) one or more metal-containing compound (s), and (iii) one or more polar organic compound solvents acting as a solvent (s) for the metal-containing compound (s), optionally together with water.

All three components can be mixed together simultaneously. The components may be mixed together at room or elevated temperature, for example, at about 20 to about 200 ° C, and at a mode of about 40 to about 80 ° C, and at a mode of about 40 to about 60 ° C.

In an alternative embodiment, two of the three components may be mixed together in a preliminary step, before the third component is added to complete the liquid mixture. Components (ii) and (iii) may be mixed together in a preliminary step. These two components can form a clear solution. Subsequently, component (i) may be added to complete the liquid mixture which may contain solid particles if component (i) is a solid support. The liquid mixture may be formed at an elevated temperature, for example from about 20 to about 200 ° C and in an embodiment of about 30 to about 80 ° C. Component (i) may be a catalyst support or catalyst support precursor. A catalyst support may be in the form of one or more solid particles. The catalyst support precursor may initially be in liquid form or in solution form. The support precursor may form a solid catalyst support in place, for example after the catalyst support precursor has been added to the liquid mixture. The catalyst support precursor may form a catalyst support in the conversion step (b) or combustion step (c). The catalyst support may be an inert support or an active support. Examples of supports that may be used may include solid oxides, carbides, zeolites, carbon and boronitride. These may include alumina, modified alumina, spinel oxides, silica, modified silica, magnesium, titania, zirconia, a molecular sieve, a zeolite, beta-aluminate and carbon forms. The alumina or modified alumina may be, for example, alpha-alumina, beta-alumina or gamma-alumina. Beta-alumina and spinel oxides such as barium hexaaluminate may be particularly useful. The carbon may be in the form of active carbon or carbon nanotubes. A zeolite may be used. The support may comprise pores or channels. Zeolites may include zeolites A, X, Y, ZSMs, MCMs, or AIP04.

Catalyst support precursors may be derived from Al (NO3) 3.9H20 or Mg (NO3) 2. Catalyst precursors that may be used are described in further detail in GOnzalez et al., Catalysis today, 35, (1997), 293-317, and J. Livage, Catalysis Today, 41 (1998), 3-19, above. The catalyst support may be derived from a nitrate, for example from a Group IIA or Group IIIA metal. For example, aluminum or magnesium nitrate may be used. Nitrate may be in a hydrated form. Examples may include Al (NO3) 3.9Η20 and Mg (NO3) 2 · 6H20. In step (a), nitrate may be mixed with an organic compound such as urea and / or ammonium citrate to form a clear solution. Water can be optionally added. To complete the liquid mixture, a metal containing compound such as cobalt nitrate may be included in the mixture. During one of the subsequent conversion and combustion steps, a supported catalyst or supported catalyst precursor may be formed. The catalyst may be porous. The particle size may be from approximately 0.1 μπι to approximately 20 mm, or from approximately 0.2 μπι to approximately 5 mm. The surface area may be greater than approximately 5 m2 / g, or greater than approximately 10 m2 / g, or greater than approximately 50 m2 / g, or greater than approximately 200 m2 / g. One or a mixture of two or more catalyst supports may be used. Component (ii) of the liquid mixture may comprise one or more metal containing compounds. The catalytically active component of the catalyst may be derived from such a metal containing compound. The metal in the metal containing compound may comprise V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W or a mixture of two or more thereof. It is also possible to incorporate an additional metal for example to act as a promoter or modifier such as at least one of Zr, U, Ti, Hf, Ce, La, Y, Mg, Ca, Sr, Cs, Rb, Mo, W, Cr, Mg, rare earth metals, noble metals, or a mixture of two or more thereof. For example, the metal containing compound may comprise at least one of V, Cr, Mn, Fe, Co, Ni, Cu, Mo or W and at least one metal selected from lanthanide, actinide and transition metal series of the Periodic Table. The additional metal may be a d-block or f-block metal. The additional metal may be one or more metals selected from noble metals such as Pd, Pt, Rh, Ru, Ir, Au, Ag and Os, and transition metal elements such as Ti, V, Cr, Mn, Fe, Co, Ni. , Cu, Zn, Zr, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg, Ti and the 4f-block lanthanides as La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Of these metals, Pd, Pt, Ru, Ni, Co, Fe, Cu, Mn, Mo and W may be particularly useful. The metal containing compound may contain other elements. The metal containing compound is in the form of a salt. Examples of metal containing salts may include nitrates, citrates, halides, alkoxides, phenoxides, acetates, benzoates, oxalates and acetyl acetonates. Component (iii) of the liquid mixture may be a polar organic compound. The organic compound may function as a solvent for component (ii) and may act as a solvent for compound (i). The organic compound may be any polar organic compound that is capable of combustion in the presence of an oxygen-containing atmosphere such as air. During combustion the organic compound may be converted to carbon which may be present as elemental carbon or as carbide, for example a metal carbide of the metal containing compound (ii). Some or all of the organic compound may be converted to carbon, and it is also possible for some of the organic compound to be completely burned such that carbon is converted to carbon monoxide or carbon dioxide and is removed from the catalyst or precursor of carbon. catalyst as gas. The organic compound may be a non-ash producing compound, in particular an oxide ash, after the combustion step. The organic compound may be one which contains no elements that tend to form residues such as oxides upon combustion. Such elements may include, for example, metals, phosphorus and / or silicon.

Examples of organic compounds which may be used include organic amines, organic carboxylic acids and salts thereof as ammonium salts, alcohols, ammonium salts of phenoxides and alkoxides, amino acids and surfactants. The alcohols may be those containing from 1 to about 30 carbon atoms, or from 1 to about 15 carbon atoms. Examples of the alcohols that may be used may include methanol, ethanol and glycol. The carboxylic acid may be citric acid or oxalic acid. Other organic compounds may be compounds containing functional groups such as one or more hydroxyl, amine, amide, carboxylic acid, ester, aldehyde, ketone, imine or imide groups. These may include urea, hydroamines, trimethyl amine, triethyl amine, tetra methyl amine chloride and tetraethyl amine chloride. Organic compounds may include EDTA, urea and / or ammonium citrate. The organic compound may be in the form of a liquid at room temperature or at the temperature at which the mixture is prepared. The organic compound may be heated before being added to the mixture. The organic compound may also be in the form of a solid at room temperature or at the temperature at which the mixture is prepared, in which case the mixture may be heated after being prepared to melt the organic compound and then dissolve the metal compound. Mixtures of organic compounds may be used. Water may also be added, for example to aid dissolution of the metal compound (s).

When water is employed in the liquid mixture, the amount of water may need to be controlled. For example, certain catalyst support precursors such as Fe (NO3) 3.9H20 and Al (NO3) 3.9H20 may tend to form gels upon contact with effective amounts of water. Thus, the amount of water employed in step (a) should be kept to a minimum to prevent formation of a hydrolyzed gel. The amount of water may be sufficient to partially hydrolyze the catalyst precursor but not sufficient to convert the catalyst precursor to a polymer. Typically up to approximately 20% water may be used with respect to the total weight of the mixture. Water may be added separately or may, for example, be present in one of the components added as crystallization water or coordinating water. The mixture may also comprise other components. These may include promoters and / or modifiers. Promoters may include alkaline earth salts such as magnesium, calcium, barium and / or strontium nitrate. Modifiers may include rare earth modifiers such as rare earth salts, for example lanthanum and / or cerium nitrate or acetate, or d-block transition metal oxides. Phosphorus, boron, gallium, germanium, arsenic and antimony oxides may be used. Promoters and modifiers may be used individually or in a combination of two or more. The mixture prepared in step (a) may be a liquid mixture. The term "liquid mixture" refers to the fact that the mixture is in the form of a homogeneous liquid, although it may comprise solid particles. For example, after mixing of homogeneous liquid of organic compounds, optionally water, and metal compounds has been formed, insoluble particles of the inert support may be added. For example, if a catalyst support instead of a catalyst support precursor is present, the liquid may comprise solid support particles. The metal containing compound must be capable of contacting the support or support precursor, and this can be obtained by using a liquid mixture. The weight ratio of component (i) :( ii) (iii) employed in step (a) may be approximately 0.1-80: 1-90: 1-99 or approximately 0.5-60: 2-80: 1-90. The weight ratios may be varied depending on the intended use of the final catalyst. The amount of organic compound can be determined by the carbon atomic ratio in the organic compound to metal (C: M) in the dissolved metal containing compound. The atomic ratio may be at least 0.4: 1 or approximately 1 to approximately 20: 1.

After formation of the liquid mixture, it can be converted to a paste or solid residue in step (b). This can be obtained by heating the mixture. This heating step may be in addition to any heating required to melt the organic compound, although if preheating is required that heating may simply be continued in step (b). heating may turn the liquid mixture into a solid, for example by evaporating or decomposing the organic solvent. Any water that may be present in the liquid mixture may be evaporative. The temperature at which the mixture is heated may be any temperature above room temperature, for example from about 50 ° C to about 250 ° C and may be performed for any time until a solid residue is formed, for example by about 1 to about 24 hours. A combination of drying steps may be used. The mixture may be initially dried at room temperature for approximately 2 to approximately 10 hours, and subsequently dried at an elevated temperature, for example from approximately 100 ° C to approximately 200 ° C or approximately 120 ° C.

In step (c) the mixture may be burned. The combustion step can be performed in the air. Alternatively, pure oxygen or oxygen in an inert atmosphere, eg nitrogen or other inert gas may be employed. This combustion step may be separated from the heating in step (b), or the two steps may be combined for example by simply continuing to heat the mixture after the solvent has been removed. The combustion temperature may be from about 200 ° C to about 1000 ° C or from about 400 ° C to about 600 ° C. The combustion step may be performed for any period of time, for example, approximately 60 minutes or less, or approximately 30 minutes or less, or approximately 15 minutes or less, or from approximately 5 to approximately 15 minutes. The combustion step can convert polar organic compound into carbon and volatiles. While not wishing to be bound by theory, it is believed that the combustion step can totally or partially change the metal containing compound into a metal and / or one or more oxides, oxycarbides or carbide forms, or mixtures of two or more thereof. . The combustion step may also convert the promoter and / or modifier to oxide forms if present. The preparation of the Fischer-Tropsch catalyst can first proceed by mixing the metal-containing compound (s) and polar organic compound (s). Such a mixture may be viscous and addition to a solid catalyst support may coat the external surface of the support with only limited penetration of "internal" surfaces such as pores. After the combustion step, a catalyst called "eggshell" in which all or substantially all catalyst may be present on the surface of the support may be obtained. This process can provide a better and more uniform distribution of the catalyst on the support surface than when only water is used as the solvent. Preparation of the Fischer-Tropsch catalyst may also proceed first by mixing the metal containing compound (s) with the organic compound (s) and then adding a soluble support. After combustion, the metal catalyst can be distributed on both the "outer" and "inner" surfaces of the support. This process can provide a more homogeneous catalyst distribution across the support than with previously known catalysts. The Fischer-Tropsch catalyst or catalyst precursor may be distributed in any desired mode on the "outer" or "inner" surfaces of the support, may be distributed substantially throughout the support or only on the external surface of the support, the component distribution Active catalyst or precursor thereof can be controlled. The Fischer-Tropsch catalyst or catalyst precursor may contain carbon in all its possible forms. For example, it may be present as elemental carbon or in the form of metal carbide or oxycarbide. The carbon content may be up to approximately 8 wt% based on the total weight of the catalyst or catalyst precursor, or from about 0.01 to about 8 wt% or from about 0.01 to about 2 wt%. The Fischer-Tropsch supported catalyst or catalyst precursor may comprise from about 0.5 to about 50% by weight of catalyst or catalyst precursor, from 0 to about 10% of promoter and from 0 to about 5% by weight of modifier. based on the total weight of the supported catalyst or catalyst precursor. The supported catalyst or catalyst precursor may comprise from about 5 to about 40 wt% catalyst or catalyst precursor, 0 to about 3 wt% promoter, and 0 to about 3 wt% modifier. The supported Fischer-Tropsch catalyst precursor can be activated with hydrogen or steam or hydrocarbon gas. The solvent may be removed by heating such that the organic compound may be deposited on the pores of the catalyst support. The catalyst support may then be mixed with the metal containing compound. Alternatively, the catalyst support may be kneaded with the metal containing compound. Such a process may produce a supported catalyst or catalyst precursor in which the catalyst or catalyst precursor may be predominantly situated on the outer surfaces of the porous particles. The alcohol forming catalyst may comprise any suitable catalyst for converting synthesis gas into one or more alcohols. The alcohol forming catalyst may comprise a catalyst metal of Nb, Ta, Mo, W, Tc, Re or a mixture of two or more thereof in free or combined form. The catalyst metal may be combined with an yttrium cocatalyst metal, a lanthanide serial metal, an actinide serial metal or a combination of two or more thereof in free form or in combined form. The alcohol forming catalyst may comprise RhAg, CuCo, CuThOx and / or CoMoS. The term "in free or combined form" means that the metal component of interest may be present as a metal, alloy, compound, adduct or combination thereof. Representative compounds include hydroxides, oxides, sulfides, sulfates, halides, carbides, cyanides, nitrides, nitrates, phosphates, borides, silicides, silicates, oxyalides, carboxylates such as acetates and acetyl acetates, oxalates, carbonates, carbonyls, hydrides, group compounds and metal bonded, compounds where the metal is part of an anionic or cationic species and the like. Adducts are chemical addition products. Electron donating or polar solvent molecules, forming solvent or ligands such as ammonia, aliphatic or aromatic amines, imines, amino alcohols, carboxylic acids, amino acids, di- and trialkyl triaryl phosphines, -arsines, and stibins and their oxides, thiols, Amino thiols, and the like, may add to the catalyst metals with or without displacement. Such catalysts are described in US Patent 4,762,858, which is incorporated herein by reference. The alcohol forming catalyst may comprise a copper or copper based modified metal synthesis catalyst, a cobalt / copper or cobalt / copper based Fischer-Tropsch catalyst, a precious metal based catalyst (e.g. Rh) or a catalyst based on Mo or MoS2. Such catalysts are described in US patents 4,122,110; 4,298,354; 4,492,773; and 4,882,360; and in Subramani et al., "A review of recent literature to search for efficient catalytic process for conversion of syngas to ethanol," Energy & Fuels XXXX, xxxx, 000-000 (2007); which are incorporated herein by reference. The alcohol forming catalyst may be used in combination with a dehydration catalyst to provide an unsaturated hydrocarbon route synthesis gas. Examples of the dehydration catalyst that may be used include acidic oxides such as alumina, silica alumina, zeolite, and synthetic silica alumino phosphate molecular sieves. These are disclosed in US 2006 / 0020155A1 and US2007 / 0244000A1, which are incorporated herein by reference. The alcohol forming catalyst and the dehydration catalyst may be mixed or combined together in the same reaction zone. Alternatively, the dehydration catalyst may be positioned downstream of the alcohol formation catalyst in the same microchannel reactor or in a separate microchannel reactor. The SMR catalyst may comprise any SMR catalyst. The SMR catalyst may comprise La, Pt, Fe, Ni, Ru, Rh, In, Ir, W, and / or an oxide thereof, or a mixture of two or more thereof. In one embodiment, the SMR catalyst may further comprise MgO, A1203, Si02, Ti02 or a mixture of two or more thereof. In one embodiment, the SMR catalyst may comprise 13.8% Rh / 6% -Mg0 / Al203 in a FeCrAIY alloy metal felt prepared using wash coating of FeCrAIY felt with a thickness of approximately 0.25 mm and approximately 0.25 mm. 90% porosity. In one embodiment, the SMR catalyst may be derived from an aqueous solution of La (No3) 3.6H20. In one embodiment, the SMR catalyst may be derived from a solution of Pt (NH3) 4 (NO3) 2. In one embodiment, the SMR catalyst may be derived from solutions of La (NO3) and Rh (NO3) which are deposited in a Pt (NH3) 4 solution. one or more Al203 layers. The combustion catalyst may comprise Pd, Pr, Pt, Rh, Ni, Cu and / or an oxide thereof, or a mixture of two or more thereof. In one embodiment, the combustion catalyst may further comprise A1203, Si02, MgO, or a mixture of two more thereof. In one embodiment, the combustion catalyst may be derived from a solution of Pd (NO3) 2 which is deposited in a layer of A1203. In one embodiment, the combustion catalyst may comprise a layer of Pr and Pd using nitrate precursors, and a layer of Pt using a solution of Pt (NH3) 4 (NO3) 2. The hydrocracking catalyst may comprise any catalyst. hydrocracking. Such catalysts may include Zeolite catalysts including beta zeolite, omega zeolite, L-zeolite, ZSM-5 zeolites and type Y zeolites. The hydrocracking catalyst may comprise one or more pillar clays, MCM-41, MCM-48, HMS , or a combination of two or more thereof. The hydrocracking catalyst may comprise Pt, Pd, Ni, Co, Mo, W or a combination of two or more thereof. The hydrocracking catalyst may include a refractory inorganic oxide such as alumina, magnesia, silica, titania, zirconia and silica alumina. The hydrocracking catalyst may comprise a hydrogenation component. Examples of suitable hydrogenation compounds include Group IVB and Group VIII metals from the Periodic Table and compounds of such metals. Molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, rhodium and ruthenium can be used as the hydrogenation component. Such catalysts are described in US Patent 6,312,586 B1, which is incorporated herein by reference. Fischer-Tropsch catalyst, alcohol formation, SMR, combustion and / or hydrocracking may be positioned in a single reaction zone or may be positioned in more than one reaction zone in the process microchannels or combustion channel. The same or different catalyst may be used in each reaction zone. The catalyst may be a graduated catalyst. In each reaction zone the length of one or more heat exchange zone (s) adjacent to or in thermal contact with the reaction zone may vary in size. For example, in one embodiment, the length of one or more of these heat exchange zones may be less than approximately 50% of the length of each reaction zone. Alternatively, one or more heat exchange zones may have lengths that are more than about 50% of the length of each reaction zone to about 100% of the length of each reaction zone. The Fischer-Tropsch catalyst, alcohol formation, SMR, combustion and / or hydrocracking can be any size and geometric configuration that fits the process microchannels. The catalyst may be in the form of particulate solids (eg pellets, dust, fibers and the like) having an average particle diameter of about 1 to about 1000 μιη (microns), and in a mode about 10 to about 500 μπι, and in a mode about 25 to about 300 μιη, and in a mode about 80 to about 300 μιη. In one embodiment, the catalyst is in the form of a fixed bed of particulate solids. The Fischer-Tropsch alcohol forming catalyst, SMR catalyst, combustion catalyst and / or hydrocracking may be in the form of a fixed bed of particulate solids (as shown in Figure 15). The particle mediating diameter of the particulate solids may be small, and the length of each process microchannel may be relatively short. The median particle diameter may be in the range from about 1 to about 1000 μιη, and in a modality approximately 10 to about 500 μιη, and the length of each process microchannel may be in the range of approximately 500 cm, and in one embodiment. about 10 to about 500 cm, and in a mode about 50 to about 300 cm.

Referring to Figure 15, catalyst 261, which is in the form of a particulate solids bed, is contained in process microchannel 260. Reagents enter the fixed bed as indicated by arrow 262, are subjected to reaction and product flows to outside the fixed bed as indicated by arrow 263. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may be supported on a porous support structure such as a foam, felt, filler or a combination thereof. The term "foam" is used herein to refer to a continuous walled structure defining pores throughout the structure. The term "felt" is used herein to refer to a fiber structure with interstitial spaces between them. The term "padding" is used herein to refer to a tangled leg structure such as steel wool. The catalyst may be supported on a honeycomb structure. The catalyst may be supported on a flow support structure such as a felt with an adjacent slack, a foam with an adjacent slack, a slack fin structure, a wash coating on any inserted substrate, or a gauze that is parallel to the direction. with a corresponding clearance for flow.

An example of a flow structure is illustrated in Figure 16. In Figure 16, catalyst 266 is contained in process microchannel 265. An open passageway 267 allows fluid to flow through process microchannel 265 as indicated by arrows 268 and 269 Reagents contact the catalyst and undergo reaction to form product. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst, and / or hydrocracking catalyst may be supported on a direct flow support structure such as a foam, filler, pellet, powder or gauze. An example of a direct flow structure is illustrated in Figure 17. In Figure 17, direct flow catalyst 271 is contained in process microchannel 270, reagents flow through catalyst 271 as indicated by arrows 272 and 273, and are subjected to to the reaction to form the product. The support structure for a direct flow catalyst may be formed of a material comprising silica gel, foamed copper, sintered stainless steel fiber, steel wool, alumina, or a combination of two more thereof. In one embodiment, the support structure may be made of a heat conductive material, such as a metal, to increase heat transfer to or from the catalyst. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst, and / or hydrocracking catalyst may be directly coated by washing on the inner walls of the process microchannels or combustion channels, grown on the channel walls at from solution, or coated in a fin structure. The catalyst may be in the form of a single piece of porous contiguous material, or many pieces in physical contact. In one embodiment, the catalyst may comprise a contiguous material and have a contiguous porosity such that molecules can diffuse through the catalyst. In this embodiment, fluids flow through the catalyst rather than around it. The cross-sectional area of the catalyst may occupy from about 1 to about 99% and in one embodiment from about 10 to about 95% of the cross-sectional area of the process microchannels and / or combustion channels. The Catalyst may have a surface area, as measured by BET, greater than approximately 0.5 m2 / g, and in a mode greater than approximately 2 m2 / g. The Fischer-Tropsch catalyst, alcohol forming catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may comprise a porous support, an interfacial layer on the porous support, and a catalyst material on the interfacial layer. The interfacial layer may be deposited in solution on the support or may be deposited by chemical vapor deposition or physical vapor deposition. In one embodiment the catalyst has a porous support, a buffer layer, an interfacial layer, and a catalyst material. Any of the above layers may be continuous or discontinuous as in the form of dots, or in the form of a layer with gaps or holes. The porous support may have a porosity of at least approximately 5% as measured by mercury porosimetry and an average pore size (sum of pore diameters divided by number of pores) of approximately 1 to approximately 1000 microns. The porous support may be a porous ceramic or a metal foam. Other porous supports that may be used include carbides, nitrides and composite materials. Porous support may have a porosity of from about 30% to about 99% and in a mode from about 60% to about 98%. The porous support may be in the form of a foam, felt, filler or a combination thereof. The open cells of the metal foam may range from approximately 20 pores per inch (ppi) to approximately 3000 ppi, and in an embodiment of approximately 20 to approximately 1000 ppi, and in an embodiment of approximately 40 to approximately 120 ppi. The term "ppi" refers to the largest number of pores per inch (in isotropic materials the measurement direction is irrelevant; however, in anisotropic materials the measurement is made in the direction that maximizes the pore number). The buffer layer, when present, may have a different composition and / or density than both the porous support and the interfacial layers, and in one embodiment has a thermal expansion coefficient that is intermediate to the thermal expansion coefficients of the porous support. interfacial layer. The buffer layer may be a metal oxide or metal carbide. The buffer layer may comprise A1203, Ti02, Si02, Zr02 or a combination thereof. A1203 may be α-Α1203, y-Al2Q3 or a combination thereof. The buffer layer may be formed of two or more sublayers of different composition. For example, when the porous support is metal, for example a stainless steel foam, a buffer layer formed of two sublayers of different composition may be used. The first sublayer (in contact with the porous support) may be Ti02. The second sublayer may be hi-A1203 which is placed over Ti02. In one embodiment, the a-A1203 sublayer is a dense layer providing protection from the underlying metal surface. A high surface area interfacial layer, less dense as alumina can then be deposited as a support for a catalytically active layer. The porous support may have a different thermal expansion coefficient than that of the interfacial layer. In such a case a buffer layer may be required to transition between the two thermal expansion coefficients. The thermal expansion coefficient of the buffer layer may be shaped by controlling its composition to obtain an expansion coefficient that is compatible with the expansion coefficients of the porous support and interfacial layers. The buffer layer should be free of openings and holes to provide superior protection of the underlying support. The buffer layer may be non-porous. The buffer layer may have a thickness that is less than half the average pore size of the porous support. The buffer layer may have a thickness of approximately 0.05 to approximately 10 μπι, and in a mode of approximately 0.05 to approximately 5 μπι.

In a suitable embodiment, adhesion and chemical stability may be obtained without a buffer layer. In this embodiment the buffer layer may be omitted. The interfacial layer may comprise nitrides, carbides, sulfides, halides, metal oxides, carbon or a combination thereof. The interfacial layer provides high surface area and / or provides a desirable support-catalyst interaction for supported catalysts. The interfacial layer may be comprised of any material that is conventionally used as a catalyst support. The interfacial layer may comprise a metal oxide. Examples of metal oxides which may be used include C 1 -C 2 Al 3 O, SiO 3, ZrC> 2, TiO 2, tungsten oxide, magnesium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, nickel oxide , cobalt oxide, copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminum oxide, lanthanum serial oxide (s), zeolite (s) and combinations thereof. The interfacial layer may serve as a catalytically active layer without any additional catalytically active material deposited thereon. The interfacial layer may be used in combination with a catalytically active layer. The interfacial layer may also be formed of two or more sublayers of different composition. The interfacial layer may have a thickness that is less than half the average pore size of the porous support. The interfacial layer thickness may range from about 0.5 to about 100 μιη, and in a mode of about 1 to about 50 microns. The interfacial layer may be crystalline or amorphous. The interfacial layer may have a BET surface area of at least about 1 m2 / g. Fischer-Tropsçh catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may be deposited on the interfacial layer. Alternatively, the catalyst material may be simultaneously deposited with the interfacial layer. The catalyst layer may be closely dispersed in the interfacial layer. The catalyst layer being "dispersed on" or "deposited on" the interfacial layer includes the conventional understanding that microscopic catalyst particles are dispersed: on the surface of the support layer (i.e., interfacial layer), in cracks in the support layer. and in open pores in the backing layer. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst, and / or hydrocracking catalyst may be supported on an assembly of one or more fins positioned within the process microchannels. Examples are illustrated in figures 18-20. Referring to Figure 18, the fin assembly 280 includes fins 281 which are mounted on the fin holder 283 which overlaps the base wall 284 of process microchannel 285. The fins 281 protrude from the fin holder 283 inwardly. of process microchannel 285. Fins 281 may extend to and contact the interior surface of upper wall 285 of process microchannels 285. Fin channels 287 between fins 281 provide passageways for reagent and product to flow through parallel process microchannel 285. at your length. Each of the fins 281 has an outer surface on each side. The outer surface provides a support base for the catalyst. Reagents may flow through fin channels 287, contact the supported catalyst on the outer surface of fins 281, and react to form the product. The flap assembly 280a shown in Figure 19 is similar to the flap assembly 280 illustrated in Figure 18 except that the flaps 281a do not extend all the way to the inner surface of the upper wall 286 of microchannel 285. The flap assembly 280b shown in Figure 20 is similar to the flap assembly 280 illustrated in Figure 18 except that the flaps 281b in the flap assembly 280b have trapezoidal cross-sectional shapes. Each of the fins may have a height ranging from approximately 0.02 mm to the height of process microchannel 285, and in an embodiment of approximately 0.02 to approximately 10 mm, and in an embodiment of approximately 0.02 to approximately 5 mm. mm, and in a mode of from about 0.02 to about 2 mm. The width of each fin may range from approximately 0.02 to approximately 5 mm, and in an embodiment of approximately 0.02 to approximately 2 mm and in an embodiment of approximately 0.02 to approximately 1 mm. The length of each fin may be of any length up to the length of process microchannel 285 and in an embodiment up to approximately 10 m, and in an embodiment approximately 0.5 to approximately 10 m, and in an embodiment approximately 0.5 to approximately 10 m. 6 m, and in one embodiment approximately 0.5 to approximately 3 m. the gap between each of the fins may be of any value and may range from approximately 0.02 to approximately 5 mm, and in an embodiment from approximately 0.02 to approximately 2 mm, and in an embodiment from approximately 0.02 to approximately 1 mm. mm The number of fins in process microchannel 285 may range from approximately 1 to about 50 fins per centimeter wide of process microchannel 285, and in a mode of approximately 1 to approximately 30 fins per centimeter, and in a mode of approximately 1 to about 10 fins per centimeter, and in a mode of about 1 to about 5 fins per centimeter, and in a mode of about 1 to about 3 fins per centimeter. Each of the fins may have a cross-section in the form of a rectangle or square as illustrated in figures 18 or 19, or a trapezoid as shown in figure 20. When viewed along its length, each fin may be straight, tapered or have a streamer setting. The flap assembly may be made of any material that provides sufficient strength, dimensional stability and heat transfer characteristics to allow operation for which the dimensional microchannel is intended. These materials include: steel (eg stainless steel, carbon steel and the like); aluminum; titanium; nickel; platinum; rhodium; copper; chrome; alloys of any of the above metals; monel; inconel; brass; polymers (for example, thermosetting resins); ceramics; glass; quartz; silicon; or a combination of two or more thereof. The Flap assembly may be made of an AI2O3 or Cr203 forming material. The vane assembly may be made of an alloy comprising Fe, Cr, Al and Y, or an alloy comprising Ni, Cr and Fe. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may be in the form of a bed of particulate material which may be graded in composition or graded with a thermally conductive inert material. The thermally conductive inert material may be interspersed with the active catalyst. Examples of thermally conductive inert materials that may be used include diamond dust, silicon carbide, aluminum, alumina, copper, graphite and the like. The catalyst bed fraction may range from approximately 100 wt% active catalyst to less than approximately 50 wt% active catalyst. The catalyst bed fraction may range from about 10% to about 90% by weight of active catalyst, and in an embodiment from about 25% to about 75% by weight. In an alternative embodiment the thermally conductive inert material may be used in the center of the catalyst or in the catalyst particles. The active catalyst may be deposited externally, internally or intermittently in a composite structure including the thermally conductive inert. The resulting composite catalyst structure can have effective thermal conductivity when placed in a process microchannel or combustion channel that is at least about 0.3 W / m / K and in a mode at least about 1 W / m / K and in a mode at least about 2 W / m / k. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may be graded only locally within the process microchannels or combustion channels. For example, a process microchannel may contain a catalyst bed with a first reaction zone and a second reaction zone. The top or bottom (or front or rear) of the catalyst bed may be graded in composition whereby a more or less active catalyst is employed in all or part of the first or second reaction zone. Composition that is reduced in a reaction zone can generate less heat per unit volume and thereby reduce the hot spot and potential for producing undesirable by-products, such as methane in a Fischer-Tropsch reaction. The catalyst may be graded with an inert material in the first and / or second reaction zone, either in whole or in part. The first reaction zone may contain a first catalyst or inert material composition, while the second reaction zone may contain a second catalyst or inert material composition.

Different particle sizes may be used in different axial regions of the process microchannels or combustion channels to provide graduated catalyst beds. For example, very small particles may be used in a first reaction zone while larger particles may be used in a second reaction zone. Average particle diameters may be less than half the height or clearance of the process microchannels. Very small particles may be smaller than a quarter of the process microchannel height or clearance. Larger particles may cause lower pressure drops per unit length of process microchannels and may also reduce catalyst effectiveness. The effective thermal conductivity of a catalyst bed may be lower for larger particles. Smaller particles may be used in regions where improved heat transfer is sought throughout the catalyst bed or alternatively larger particles may be used to reduce the local rate of heat generation.

Relatively short contact times, high desired product selectivity and relatively low catalyst deactivation rates can be obtained by thresholding the required diffusion path for the catalyst. This can be achieved when the catalyst is in the form of a thin layer on a support constructed as a metal foam or on the wall of the process microchannel. This may allow increased space speeds. The thin layer of catalyst can be produced using chemical vapor deposition. This thin layer may have a thickness in the range of up to approximately 1 micron, and in a mode in the range of approximately 0.1 to approximately 1 micron, and in a mode in the range of approximately 0.1 to approximately 0.5 micron, and in one mode approximately 0.25 micron. These thin layers can reduce the time reagents are within the active catalyst structure by reducing the diffusion path. This may decrease the time reagents spend in the active portion of the catalyst. The result can be increased product selectivity and reduced unwanted by-products. An advantage of this mode of catalyst use may be that, unlike conventional catalysts in which the active portion of the catalyst may be bonded to an inert low thermal conductivity binder, the active catalyst film may be in intimate contact with a constructed structure. or a wall of the process microchannel. This can leverage high heat transfer rates obtainable in the microchannel reactor and allow close temperature control. This can result in the ability to operate at increased temperature (faster kinetics) without promoting the formation of undesirable byproducts, thereby producing higher productivity and yield and extending catalyst life. The configuration of the SMR 500 microchannel reactor, hydrocracking microchannel reactor 700, and / or the Fischer-Tropsch 200 microchannel reactor may be molded to match the reaction kinetics. Near the inlet or top of a first reaction zone of a process microchannel, the height or clearance of the microchannel may be less than in a second reaction zone near the outlet or bottom of the process microchannel. Alternatively, the reaction zones may be less than half the process microchannel length. For example, a first process microchannel height or backlash may be used for the first 25%, 50%, 75%, or 90% of the process microchannel length for a first reaction zone, while a second or greater second height or backlash may be used. be used in a second downstream reaction zone from the first reaction zone. This setting may be appropriate for conducting Fischer-Tropsch reactions or alcohol formation. Other gradations in process microchannel height or clearance may be used. For example, a first height or clearance may be used near the microchannel inlet to provide a first reaction zone, a second height or clearance downstream from the first reaction zone may be used to provide a second reaction zone, and a third height or clearance may be used to provide a third reaction zone near the microchannel outlet. The first and third heights or clearances may be the same or different. The first and third heights or clearances may be larger or smaller than the second height or clearance. The third height or clearance may be smaller or greater than the second height or clearance. The second height or clearance may be greater or less than the third height or clearance. Fischer-Tropsch catalyst, alcohol formation catalyst, SMR catalyst, combustion catalyst and / or hydrocracking catalyst may be regenerated by flowing a regeneration fluid through the channels in contact with the catalyst. The regeneration fluid may comprise hydrogen or a dilute hydrogen flow. The diluent may comprise nitrogen, argon, helium, methane, carbon dioxide, vapor or a mixture of two or more thereof. The temperature of the regenerating fluid may be from about 50 to about 400 ° C, and in an embodiment from about 200 to about 350 ° C. The pressure in the channels during this regeneration step can range from about 1 to about 40 atmospheres, and in a mode of about 1 to about 20 atmospheres, and in a mode of about 1 to about 5 atmospheres. The residence time for the regenerating fluid in the channels may range from approximately 0.01 to approximately 1000 seconds, and in an embodiment from approximately 0.1 second to approximately 100 seconds.

When the catalyst is a Fischer-Tropsch catalyst, it may be regenerated by increasing the molar ratio of H2 to CO in the reagent composition to at least about 2.5: 1, and in a mode at least about 3: 1, and flowing to resultant adjusted feed composition through the process microchannels in contact with the catalyst at a temperature in the range of approximately 150 ° C to approximately 300 ° C, and in a mode in the range of approximately 180 ° C to approximately 250 ° C for a period of time. from about 0.1 to about 100 hours, and in a mode from about 0.5 to about 20 hours, to provide the regenerated catalyst. The feed composition can be adjusted by stopping the flow of all feed gases except hydrogen and flowing hydrogen through the process microchannels in contact with the catalyst. The flow of H2 may be increased to provide the same contact time as used for the reagent composition comprising H2 and CO. The adjusted feed composition may comprise H2 and is characterized by the absence of CO.

After catalyst regeneration, the Fischer-Tropsch process may be continued by contacting the regenerated catalyst with the original reagent composition comprising H2 and CO.

Fischer-Tropsch alcohol-forming process microchannels, SMR process microchannels, combustion channels, and / or hydrocracking process microchannels may be characterized by having volume flow paths. The term "volume flow path" refers to an open path (contiguous volume flow region) within the process microchannels or combustion channel. A contiguous volume flow region allows rapid fluid flow through the channels without large pressure drops. In one embodiment, the fluid flow in the volume flow region is laminar. Volume flow regions in each process microchannel or combustion channel may have a cross-sectional area of approximately 0.05 to approximately 10,000 mm2, and in an embodiment of approximately 0.05 to approximately 5000 mm2 and in an embodiment of approximately 0 , 1 to approximately 2500 mm 2. Volume flow regions may comprise from about 5% to about 95% and in a mode of from about 30% to about 80% of the cross-section of the process microchannels or combustion channel. The contact time of the reagents with the Fischer-Tropsch or alcohol-forming catalyst, SMR catalyst and / or combustion catalyst may range from approximately 2000 milliseconds (ms), and in the range of about 10 to about 2000 ms, and within from about 10 ms to about 1000 ms, and in a mode from about 20 ms to about 500 ms. In one embodiment, the contact time may range up to about 300 ms, and in a mode of about 20 to about 300 ms, and in a mode of about 50 to about 150 ms, and in a mode of about 75 to about 125 ms. , and in a mode about 100 ms. In one embodiment, the contact time may be up to about 100 ms, and in a mode from about 10 to about 100 ms. The space velocity (or gas hourly space velocity (GHSV)) for fluid flow in the alcohol-forming or Fischer-Tropsch process microchannels, MSR process microchannels and / or combustion channels may be at least approximately 1000 hr. ”1 (normal feed liters / hour / liter volume in process microchannels) or at least approximately 800 ml feed / (g catalyst) (h). space velocity may range from approximately 1000 to approximately 1,000,000 hr-1, or from approximately 800 to approximately 800,000 ml feed / (g catalyst) (h). In one embodiment, the space velocity may range from approximately 10,000 to approximately 100,000 hr-1 or approximately 8,000 to approximately 80,000 ml feed / (g catalyst) (h). The hourly liquid space velocity (LHSV) for fluid flow in the hydrocracking microchannel reactor may be in the range of approximately 0.1 to approximately 100 hr-1 (feed volume / hr / catalyst volume), and in a about 1 to about 100 hr-1, and about 5 to about 100 hr-1, and about 10 to about 100 hr-1, and about 1 to about 50 hr '1 and in a mode of from about 5 to about 50 hr-1' The pressure in the alcohol forming or Fischer-Tropsch microchannels, SMR process microchannels and / or hydrocracking process microchannels may be up to approximately 100 atmospheres, and in a mode in the range of about 1 to about 100 atmospheres, and in a mode of about 1 to about 75 atmospheres, and in a mode of about 2 to approximately 40 atmospheres, and in a mode of about 2 to about 10 atmospheres, and in a mode of about 10 to about 50 atmospheres, and in a mode of about 20 to about 30 atmospheres. The pressure drop of fluids as they flow into the alcohol or Fischer-Tropsch process microchannels, SMR process microchannels, combustion channels, and / or hydrocracking process microchannels can vary up to approximately 10 atmospheres per meter in length. (atm / m), and in a mode up to about 5 atm / m, and in a mode up to about 3 atm / m. The Reynolds number for fluid flow in the alcohol-forming or Fischer-Tropsch process microchannels, SMR process microchannels, combustion channels, and / or hydrocracking process microchannels may be in the range of from about 10 to about 4000, and in a mode of about 100 to about 2000. The average temperature in the Fischer-Tropsch process microchannels may be in the range of about 150 to about 300 ° C, and in a mode of about 200 to about 300 ° C. The average temperature in the alcohol forming process microchannels may be in the range of about 200 to about 500 ° C, and in a mode in the range of about 200 to about 350 ° C. The average temperature in the SMR microchannels may be in the range of about 100 to about 400 ° C, and in a mode in the range of about 150 to about 350 ° C. The average temperature in the hydrocracking process microchannels may be in the range of approximately 100 ° C to approximately 700 ° C, and in a mode of approximately 250 ° C to approximately 500 ° C, and in a mode of approximately 350 ° C to approximately 450 ° C and in an embodiment from approximately 370 ° C to approximately 400 ° C. Heat exchange fluid entering the heat exchange channels of the Fischer-Tropsch 200 alcohol-forming microchannel reactor and optionally hydrocracking microchannel reactor 700 may be at a temperature of from about 100 ° C to about 400 ° C. , and in a mode about 200 ° C to about 300 ° C. The heat exchange fluid exiting the heat exchange channels may be at a temperature in the range of approximately 150 ° C to approximately 450 ° C, and in a mode of approximately 200 ° C to approximately 350 ° C. The heat exchange fluid residence time in the heat exchange channels may range from about 1 to about 2000 ms, and in a mode of about 10 to about 500 ms. The pressure drop for the heat exchange fluid as it flows through the heat exchange channels may vary up to approximately 10 atm / m, and in a mode from about 1 to about 10 atm / m, and in a mode of heat transfer. approximately 2 to approximately 5 atm / m. The heat exchange fluid may be in the form of a vapor, a liquid or a mixture of steam and liquid. The Reynolds Number for heat exchange fluid flow in the heat exchange channels can be from about 10 to about 4000, and in a mode from about 100 to about 2000. The heat exchange fluid used in the heat exchange channels. in the Fischer-Tropsch 200 microchannel reactor and, optionally, hydrocracking microchannel reactor 700 may be any heat exchange fluid suitable for cooling a Fischer-Tropsch exothermic reaction. These may include air, steam, liquid water, gaseous nitrogen, other gases including inert gases, carbon monoxide, oils such as mineral oil, and heat exchange fluids such as DowthermA and Therminol which are available from Dow-Union Carbide.

The heat exchange channels used in the Fischer-Tropsch 200 alcohol-forming microchannel reactor and optionally in the hydrocracking microchannel reactor 700 may comprise process channels in which an endothermic process is conducted. These heat exchange process channels may be microchannel. Examples of endothermic processes that can be conducted in heat exchange channels include steam reforming and dehydrogenation reactions. Steam reforming of an alcohol occurring at a temperature in the range of from about 200 ° C to about 300 ° C is an example of an endothermic process that can be used. Incorporating a simultaneous endothermic reaction to provide an improved heat sink can allow a typical heat flux to be approximately one order of magnitude above the convective cooling heat flux. The heat exchange fluid may be subjected to a partial or total phase change as it flows through the heat exchanger channels of the Fischer-Tropsch 200 alcohol-forming microchannel reactor and optionally into the hydrocracking microchannel reactor 700. This phase shift can provide additional heat removal from process microchannels beyond that provided by convective cooling. For a liquid heat exchange fluid being vaporized, additional heat being transferred from the Fischer-Tropsch process microchannels and optionally from the hydrocracking process microchannels may result from the latent heat of vaporization required by the heat exchanger fluid. heat. In one embodiment, approximately 50% by weight of the heat exchange fluid may be sprayed, and in an embodiment approximately 35% by weight may be sprayed, and in an embodiment approximately 20% by weight may be sprayed, and in an embodiment approximately. 10% by weight may be sprayed. In one embodiment, approximately 10% to approximately 50% by weight may be sprayed. The heat exchange heat flow in the Fischer-Tropsch 200 alcohol-forming microchannel reactor, the SMR 500 microchannel reactor, and / or the hydrocracking microchannel reactor 700 may be in the range of approximately 0.01 to approximately 500. watts per square centimeter of surface area of one or more process microchannel heat transfer walls (W / cm2) in the microchannel reactor, and in a mode in the range of approximately 0.1 to approximately 250 W / cm2, and in a mode of from about 1 to about 125 W / cm2. The heat flux for convective heat exchange in the microchannel reactor may be in the range of approximately 0.01 to approximately 250 W / cm2 and in one embodiment in the range of approximately 0.1 to approximately 50 W / cm2, and in one embodiment. from about 1 to about 25 W / cm2, and in a mode from about 1 to about 10 W / cm2. The phase change heat flux and / or an exothermic or endothermic heat exchange fluid reaction may be in the range of from about 0.01 to about 500 W / cm2 and in a mode of from about 1 to about 250 W / cm2. and in a mode of from about 1 to about 100 W / cm2 and in a mode of from about 1 to about 50 W / cm2 and in a mode of from about 1 to about 25 W / cm2 and in a mode of from about 1 to about 10 W / cm2. Heat exchange control 'during the Alcohol or Fischer-Tropsch reaction process, SMR process and / or optionally the hydrocracking process may be advantageous to control selectivity towards the desired product due to the fact that such cooling and / or added heating may reduce or eliminate the formation of unwanted byproducts from unwanted side reactions with higher activation energies. The pressure in each individual heat exchange channel in the Fischer-Tropsch 200 or Micro-channel microchannel reactor and optionally in the hydrocracking microchannel reactor 700 can be controlled using passive structures (eg, obstructions), holes and / or mechanisms upstream of the heat exchange channels or channels. By controlling the pressure in each heat exchange microchannel, the temperature in each heat exchange microchannel can be controlled. Higher inlet pressure for each heat exchange channel may be used where passive structures, holes and / or mechanisms lower the pressure to the desired pressure. By controlling the temperature in each heat exchange channel, the temperature in the alcohol-forming or Fischer-Tropsch microchannels or hydrocracking process microchannels can be controlled. Thus, for example, each alcohol-forming process or Fischer-Tropsch microchannel may be operated at a desired temperature by employing a specific pressure in the heat exchange channel adjacent to or in thermal contact with the process microchannel. This provides the advantage of precisely controlled temperatures for each Fischer-Tropsch or alcohol-forming process microchannel. The use of precisely controlled temperatures for each alcohol-forming or Fischer-Tropsch microchannel provides the advantage of a molded temperature profile and an overall reduction in energy requirements for the process.

In a magnifying device, for certain applications, it may be necessary for the process fluid mass to be evenly distributed between the microchannels. Such an application may be when it is necessary for the process fluid to be heated or cooled with adjacent heat exchange channels. Uniform mass flow distribution can be obtained by shifting the cross-sectional area from a parallel microchannel to another microchannel. Uniformity of mass flow distribution can be defined by Quality Index Factor (Q-factor) as indicated below. A Q-factor of 0% means absolute uniform distribution.

A change in cross-sectional area may result in a difference in wall shear stress. In one embodiment, the Q-factor for hydrocracking microchannel reactor 700, SMR 500 microchannel reactor and / or Fischer-Tropsch 200 microchannel reactor may be less than approximately 50%, and in one embodiment less than about 20% and in a mode of less than about 5% and in a mode of less than about 1%. The surface velocity for fluid flowing into the alcohol-forming or Fischer-Tropsch microchannels, SMR process microchannels, and / or hydrocracking process microchannels may be at least about 0.01 meter per second (m / s), and in a mode at least about 0.1 m / s, and in a mode in the range of about 0.01 to about 100 m / s, and in a mode in the range of about 0.01 to about 1 m / s, and in a mode in the range from about 0.1 to about 10 m / s, and in a mode in the range from about 1 to about 100 m / s. The free flow rate for fluid flowing into the alcohol-forming or Fischer-Tropsch microchannels, SMR process microchannels, and / or hydrocracking process microchannels may be at least approximately 0.001 m / s, and in one embodiment at approximately 0.01 m / s, and in a mode in the range from about 0.001 to approximately 200 m / s, and in a mode in the range from about 0.01 to approximately 100 m / s, and in a mode in the range approximately 0.01 to approximately 200 m / s. Δ CO conversion in the alcohol-forming or Fischer-Tropsch reactor may be approximately 40% or higher per cycle, and in approximately 50% or higher mode, and in approximately 55% or higher mode, and at about 60% or higher mode, and at about 65% or higher mode, and at about 70% or higher mode. The term "cycle" is used herein to refer to a single passage of reagents through process microchannels. Selectivity to methane in the Fischer-Tropsch (FT) product may be approximately 25% or less, and in an approximately 20% or less mode, and in an approximately 15% or less mode, and in an approximately 12% or less mode, and in a mode about 10% or less. The yield of Fischer-Tropsch product may be approximately 25% or higher per cycle, and in an approximately 30% or higher embodiment, and in an approximately 40% or higher embodiment per cycle.

In one embodiment of the Fischer-Tropsch process, CO conversion is at least about 50%, methane selectivity is about 15% or less, and product yield is at least about 35% per cycle. Nitrogen separator 300 may comprise a microchannel separator employing an ionic liquid as a liquid absorber. The microchannel separator may comprise a thin film separator wherein the flow of the liquid absorber (i.e. the ionic liquid) is retained or confined in a channel or structure by capillary forces or forces that minimize mixing or countermixing of a liquid and a gas (For example, air) in a microchannel. The microchannel separator may comprise a device wherein a mixture of liquid absorbent fluid and gas are co-fed into or out of the microchannel device and flow in a co-flow arrangement. The fluid may flow in and out of surface features in the device. The microchannel separator may comprise a device where gas and liquid absorber flow in a co-flow arrangement and are mixed to create a high flowing interfacial area in addition to a series of obstructions in the form of a porous sealed bed of rings, spheres or other formats. The microchannel separator may comprise a device wherein a thin contact plate separates the phases to assist with countercurrent flow. The contact plate may have sufficiently small openings such that the capillary pressure of the liquid retains liquid on one side of the contact plate and gas flow on the other side of the contact plate. The ionic liquid that may be used as the liquid absorber may comprise one or more quaternary imidazole salts, and / or one or more quaternary aromatic 5- or 6-membered ring heterocyclic compounds such as imidazolium salts, pyridinium salts, and the like. These may include 1-butyl-3-methyl imidazolium hexafluorophosphate, 1-octyl 3-methyl imidazolium hexafluorophosphate, 1-butyl-3-methyl imidazolium nitrate, 1-octyl -3-methyl imidazolium tetrafluoroborate, 1-ethyl -3-methyl imidazolium ethylsulfate, and / or N-butyl pyridinium tetrafluoroborate. Ionic liquids that may be used are disclosed in US 6,579,343 B2 and 6,623,659 B2, US patent publication 2006/0251588 A1, and international publication WO 02/34863 A1, such patents and publications being incorporated herein by reference. .

Temperature oscillation adsorption (TSA) or pressure oscillation adsorption (PSA) techniques can be used in the nitrogen separator 300. TSA and PSA processes employing microchannel technology that can be used for. the above separations are disclosed in US 6,508,862 B1 and 6,552,627 B1, and US patent publication 2005/0045030 A1 which are incorporated herein by reference.

The ionic liquid separators, TSA separators and / or PSA separators discussed above may also be used in the line between gasifier 110 and microchannel separators 200 to separate contaminant gases and materials (eg, CO2, sulfur compounds such as H2S). , particulate solids and the like) from the synthesis gas formed in the gasifier 110.

Microchannel devices employing nanofiber layers or nano-composite films may be employed in the line between gasifier 110 and microchannel reactor 200 to separate contaminant materials from the synthesis gas. Nanofibers and nanocomposite films that may be used are disclosed in US 6,326,326 Bl; 6,531,224 Bl; 6,733,835 B2; 6,735,038 B21; 6,846,554 B2; and 7,122,106 B2; which are incorporated herein by reference. The presence of contaminants such as sulfur, halogen, selenium, phosphorus, arsenic and the like in the synthesis gas flowing out of gasifier 110 may be undesirable. The above contaminants may be removed from the synthesis gas or have their concentrations reduced before conducting the reaction in the microchannel reactor 200. Techniques for removing or reducing the level of these contaminants are well known to those skilled in the art. For example, ZnO protective beds may be used in the line between gasifier 110 and microchannel reactor 200 to remove sulfur impurities. The contaminant level in the synthesis gas may be reduced to a level of up to approximately 5% by volume, and in a mode up to approximately 1% by volume, and in a mode up to approximately 0.1% by volume and in a mode up to approximately 1% by volume. approximately 0.05% by volume. The pyrolysis process that is conducted in the pyrolysis reactor 400 may comprise heating the carbonaceous material in the absence of oxygen or any other reagent except possibly vapor. The pyrolysis process may comprise an anhydrous process. The pyrolysis process may comprise an instantaneous or rapid pyrolysis process wherein the carbonaceous material is heated at a temperature in the range of approximately 350 ° C to approximately 500 ° C for a relatively short period of time up to approximately 2 seconds, and in a mode in the range of about 0.5 to about 2 seconds. The pyrolysis process may be used to produce a liquid product which may be referred to as pyrolytic oil. The pyrolysis process may be conducted in a drill reactor, ablation reactor, spinning cone, fluidized bed or circulating fluidized bed. The pyrolysis reaction that is conducted in a drill reactor involves the use of a hot sand feed and particles of carbonaceous material at one end of a screw. The screw mixes the sand and carbonaceous material and carries it along as the pyrolysis process proceeds. The ablation process involves projecting particles of carbonaceous material at high speed against a hot metal surface. This can be achieved by using a metal surface rotating at high speed in a bed of carbonaceous particle material. Alternatively, the particles may be suspended in a carrier gas and introduced at high speed through a cyclone whose wall is heated. The rotating cone process involves heating a mixture of sand and particles of carbonaceous material and introducing the mixture into a rotating cone. Due to the rotation of the cone, the mixture of sand and carbonaceous material is conveyed across the surface of the cone by centrifugal force as the pyrolysis process proceeds.

With the fluidized bed reactor, particles of carbonaceous material are introduced into a gas fluidized hot sand bed. High heat transfer rates from fluidized sand result in rapid heating of carbonaceous material particles. Heat can be supplied by heat exchanger tubes through which hot flue gas can flow.

With the circulating fluidized beds, particles of carbonaceous material are introduced into a circulating fluidized bed of hot sand. Gas, sand and particles of carbonaceous material move together. The carrier gas may be a recirculated product gas, although it may also be a flue gas. High heat transfer rates from the sand provide rapid heating of carbonaceous material particles. A separator may separate product gases and vapors from sand and char particles. The sand particles can be reheated in a fluidized burner container and recycled to the reactor. The Fischer-Tropsch product formed in the microchannel reactor 200 may comprise a gas product fraction and a liquid product fraction. The gas product fraction may include boiling hydrocarbons below about 350 ° C at atmospheric pressure (e.g. tail gases through middle distillates). The liquid product fraction (the condensate fraction) may include boiling hydrocarbons above about 350 ° C (for example, vacuum gas oil through heavy paraffins). The boiling Fischer-Tropsch product fraction below approximately 350 ° C may be separated into a residual gas fraction and a condensate fraction, for example, normal paraffins of approximately 5 to about 20 carbon atoms and more boiling hydrocarbons. using, for example, a high pressure and / or lower temperature liquid vapor separator, or low pressure separators or a combination of separators. The boiling fraction above about 350 ° C (the condensate fraction) may be separated into a boiling wax fraction in the range of about 350 ° C to about 650 ° C after removing one or more boiling fractions above about 650 ° C. ° C. the wax fraction may contain linear paraffins of from about 20 to about 50 carbon atoms with relatively small amounts of higher boiling branched paraffins. Separation may be effected using fractional distillation. The Fischer-Tropsch product formed in the microchannel reactor 200 may include methane, wax and other heavy, high molecular weight products. The product may include olefins such as ethylene, iso-paraffins and normal paraffins and combinations thereof. These may include hydrocarbons in the distilled fuel ranges, including diesel or jet fuel ranges. Branching can be advantageous in a number of end uses, particularly when increased octane values and / or decreased pour points are desired. The degree of isomerization may be greater than approximately 1 mol of isoparaffin per mole of n-paraffin, and in one embodiment approximately 3 moles of isoparaffin per mole of n-paraffin. When used in a diesel fuel composition, the product may comprise a hydrocarbon mixture having a cetane number of at least about 60. The Fischer-Tropsch product may be further processed to form a lubricating base oil or diesel fuel. For example, the product made in the microchannel reactor 200 may be hydrocracked and then subjected to distillation and / or catalytic isomerization to provide a lubricating base oil, diesel fuel, aviation fuel and the like. Fischer-Tropsch product may be hydroisomerized using the process disclosed in US 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using the process disclosed in UIS patents 4,943,672 or 6,096,940; waxed off using the process disclosed in U.S. Patent 5,882,505; or hydroisomerized and waxed using the process disclosed in U.S. Patent Nos. 6,013,171, 6,080,301 or 6,165,949. These patents are incorporated herein by reference for their disclosures of processes for treating Fischer-Tropsch synthesized hydrocarbons and the resulting products made of such processes. The hydrocracking reaction conducted on the hydrocracking microchannel reactor 700 may involve a reaction between hydrogen and the Fischer-Tropsch product flowing from the microchannel reactor 200, or one or more hydrocarbons separated from the Fischer-Tropsch product (for example, a or more Fischer-Tropsch hydrocarbons from wax or liquid). The Fischer-Tropsch product may comprise one or more long chain hydrocarbons. In the hydrocracking process, a desired diesel fraction, for example, may be increased by cracking a C23 fraction to mid-range carbon numbers from C12 to C22. A wax fraction produced from the Fischer-Tropsch 200 microchannel reactor may be fed to the excess hydrogen hydrocracking microchannel reactor 700 for a triple phase reaction. Under reaction conditions at elevated temperatures and pressures, a fraction of the liquid feed may convert to a gas phase, while the remaining liquid fraction may flow through the catalyst. In conventional hydrocracking systems, a flow of liquid forms. The use of a microchannel reactor for the hydrocracking reaction provides unique advantages on several fronts. These may include kinetics, pressure drop, heat transfer, and mass transfer.

Fischer-Tropsch hydrocarbon products which may be hydrocracked in hydrocracking microchannel reactor 700 may comprise any hydrocarbon that may be hydrocracking. These may include hydrocarbons containing one or more C-C bonds capable of being disrupted in a hydrocracking process. Hydrocarbons which may be hydrocracked may include saturated aliphatic compounds (e.g. alkanes), unsaturated aliphatic compounds (e.g. alkenes, alkynes), hydrocarbyl (e.g. alkyl), substituted aromatic compounds, hydrocarbylene (e.g. alkylene), substituted aromatic compounds and the like. The feed composition for hydrocracking microchannel reactor 700 may include one or more diluent materials. Examples of such diluents may include non-reactive hydrocarbon diluents, and the like. The diluent concentration may be in the range of from zero to approximately 99% by weight based on the weight of the Fischer-Tropsch product, and in a mode of zero to approximately 75% by weight, and in a mode of zero to approximately 50% by weight. Weight. Diluents may be used to reduce the viscosity of viscous liquid reagents. The viscosity of the feed composition in the hydrocracking microchannel reactor 700 may be in the range of approximately 0.001 to approximately 1 centipoise, and in an embodiment of approximately 0.01 to approximately 1 centipoise, and in an embodiment of approximately 0.1 to approximately 1 centipoise. 1 centipoise. The ratio of hydrogen to Fischer-Tropsch product in the feed composition entering the hydrocracking microchannel reactor 700 may be in the range of from about 10 to about 2000 standard cubic centimeters (sccm) of hydrogen per cubic centimeter (cm3) of Fischer-Tropsch product. Tropsch, and in a mode of about 100 to about 1800 sccm / cm3, and in a mode of about 350 to about 1200 sccm / cm3. The hydrogen feed may further comprise water, methane, carbon dioxide, carbon monoxide and / or nitrogen. H2 in the hydrogen feed can be derived from another process such as a steam reforming process (H2 / CO molar ratio product flow of approximately 3), a partial oxidation process (H2 / molar ratio product flow C0 approximately 2), an autothermal reforming process (H2 / CO0 molar ratio product flow of approximately 2.5), CO 2 reforming (H2 / CO molar ratio product flow of approximately 1) , a coal gasification process (H2 / CO molar ratio product flow of approximately 1) and combinations thereof. With each of these ο H2 feed streams it can be separated from the remaining ingredients using conventional techniques such as membranes or adsorption. The hydrocracked Fischer-Tropsch product may comprise an average distillate fraction in the range of approximately 127-371 ° C. The term "middle distillate" is intended to include the boiling range fractions of diesel, jet fuel and kerosene. The terms of the "kerosene" and "jet fuel" boiling range are intended to refer to a temperature range of 127-288 ° C and the "diesel" boiling range are to refer to hydrocarbon boiling points between approximately 127-371 ° C. The hydrocracked Fischer-Tropsch product may comprise a fraction of gasoline or naphtha. These can be considered to be C5 at end point fractions of 204 ° C. The desired alcohol forming process product may comprise one or more alcohols having from 1 to about 10 carbon atoms, and in a embodiment of from 1 to about 5 carbon atoms, and in a embodiment from 2 to about 5 carbon atoms. carbon. The product may comprise methanol. The product may comprise methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, or a mixture of two or more thereof. These alcohols and alcohol mixtures may be used as fuels and fuel supplements. For example, these alcohols may be additional to gasoline to supplement gasoline.

Example 1 A process simulation using Chem CAD is conducted. The process is illustrated in Figure 28. Referring to Figure 28, process 600 involves the use of dryer 601, mixer 607, carbonator 610, tempering chamber 615, superheater 620, blast chilling chamber 625, scrubber 630, cyclone 635 , 640, 645 and 650 capacitors, mixer 655, Fischer-Tropsch (FT) 660 microchannel reactor, heat exchange steam circuit 663, separators 670 and 675, mixer 680 and fractionators 685 and 690. The process also employs the use of heat exchangers 636, 641, 646, 656, 673 and 674. These heat exchangers may be microchannel heat exchangers. Compressors 642, 647 and 652 are also employed in the illustrated process. The temperature, pressure, flow rate and composition of the various flows employed in process 600 are shown in the following tables 1 to 3. The operation of process 600 illustrated in figure 28 will now be described. In the following description, temperatures and pressures of various flows are indicated in parentheses. Temperatures are in ° C and pressures are in bar. In some cases, these values have been rounded from what was produced by the Chem CAD simulation. The full values produced by Chem CAD are shown in tables 1-3. Municipal solid waste (MSW) with a water content of 70% by weight flows through line 602 (15 ° C, 1 bar) into dryer 601 where the MSW is condensed. Separate water flows out of dryer 601 through line 604 (89 ° C, 1 bar). Steam flows through line 603 (250 ° C, 25 bar) into dryer 601, heats the MSW, and flows out of dryer 601 through line 605 (225 ° C, 25 bar). Condensed MSW with a 14.2 wt% water concentration flows through line 606 (89 ° C, 1 bar) into mixer 607 where it is combined with light fractionator ends from line 687 (121 ° C, 18 bar) and 692 (121 ° C, 18 bar) line fractionator bottoms. The combined flow of condensed MSW, light fractionator ends and fractionator bottoms (which may be referred to as a combined carbonacea feed) flows from mixer 607 through line 608 (94 ° C, 1 bar) to gasifier 610. Oxygen (15 ° C, 1 bar) flows through line 609 to gasifier 610. In gasifier 610, the combined carbonaceous feed and oxygen are heated and undergo a gasification reaction to form synthesis gas. Ash is removed from gasifier 610 as indicated by arrow 617. Synthesis gas flows from gasifier 610 through line 611 (1480 ° C, 1 bar) to quench chamber 615. Water flows through lines 612 and 614 ( 15 ° C, 1 bar) to quench chamber 615. Steam flows out of quench chamber 615 through line 619. Synthesis gas flows from quench chamber 615 through line 616 (1013 ° C, 1 bar) to superheater 620. Steam flows through line 618 (225 ° C, 25 bar) to and through superheater 620, and then out of superheater 620 through line 621 (450 ° C, 25 bar). Synthesis gas flows from superheater 620 through line 622 (235 ° C, 1 bar) to and through blast chilling chamber 625. Water flows through lines 612 and 613 (15 ° C, 1 bar) to and through the blast chilling chamber 625, and then out of the blast chilling chamber 625 through line 627 (67 ° C, 1 bar). Synthesis gas flows from blast chilling chamber 625 through line 626 (67 ° C, 1 bar) into scrubber 630. Contaminants are separated from synthesis gas in scrubber 630 and flow out of scrubber through line 632 (67 ° C, 1 bar). Synthesis gas flows from scrubber 630 through line 631 (67 ° C, 1 bar) into cyclone 635. Solid particulate material is separated from synthesis gas in cyclone 635. Solid particulate material is removed through line 638. Synthesis gas flows from cyclone 635 through line 637 (67 ° C, 1 bar) to and through heat exchanger 636, and then through line 637a (24 ° C, 1 bar) to inside capacitor 640 where it is condensed. Water flows out of condenser 640 through line 644 (24 ° C, 1 bar). Synthesis gas flows from capacitor 640 through line 643 (24 ° C, 1 bar) to and through compressor 642, and then from compressor 642 through line 643a (125 ° C, 2.6 bar) to and through heat exchanger 641. Synthesis gas flows from heat exchanger 641 through line 643b (24 ° C, 2.6 bar) to condenser 645 where it is condensed. Water is removed from the synthesis gas in condenser 645 and flows out of the condenser through line 648 (24 ° C, 2.6 bar). Synthesis gas flows from condenser 645 through line 649 (24 ° C, 2.6 bar) to and through compressor 647, and then from compressor 647 through line 649a (101 ° C, 5.5 bar) to and through heat exchanger 646. Synthesis gas flows from heat exchanger 646 through line 649b (24 ° C, 5.5 bar) to condenser 650 where it is condensed. Water flows out of condenser 650 through line 651a (24 ° C, 1 bar). Synthesis gas flows out of condenser 650 through line 651 (24 ° C, 5.5 bar) to and through compressor 652. Synthesis gas flows from compressor 652 through line 653 (234 ° C, 25 bar) for mixer 655. Synthesis gas flowing through line 653 has a H2: C0 ratio of 0.989. Hydrogen flows through line 654 (37 ° C, 15 bar) to mixer 655 where it is combined with the synthesis gas. The combined synthesis and hydrogen mixture may be mentioned as benefited synthesis gas. The benefited synthesis gas has a H2: CO ratio of 1.896. Benefited synthesis gas flows from mixer 655 through heat exchanger 656, and from heat exchanger 656 through line 657 (220 ° C, 25 bar) to and through the Fischer-Tropsch (FT) microchannel reactor ) 660 where the synthesis gas is subjected to an exothermic FT reaction to form an FT product. The FT 660 microchannel reactor is cooled by steam flowing through the refrigerant vapor circuit 663. Steam enters the refrigerant vapor circuit 663 through line 664 (150 ° C, 26 bar) and flows into the mixer 664a. steam flows from mixer 664a through line 664b (222 ° C, 26 bar) to and through heat exchanger 668. Heat exchanger 668 is in thermal contact with FT 660 microchannel reactor and heat exchanges with reactor of FT microchannels. steam cools the FT 660 microchannel reactor as the synthesis gas is converted to the FT product in the FT 660 microchannel reactor. Steam flows out of heat exchanger 668 through line 664c (225 ° C, 25 bar) to vapor 666. Vapor flows out of vessel 666 through line 665 (225 ° C, 25 bar) and out of refrigerant vapor circuit 663. Steam flows from vessel 666 through line 664d (225 ° C , 25 bar) to and through pump 667. Steam flows from pump 667 through line 669 (225 ° C, 27 bar) to mixer 664a. The FT product flows from the FT 660 microchannel reactor through line 661 (230 ° C, 18 bar) to separator 670 where it is subjected to separation. A gaseous FT product flows out of separator 670 through line 671 (230 ° C, 18 bar). A liquid FT product flows out of separator 670 through line 672 (230 ° C, 18 bar) to mixer 680. Gaseous FT product flows through heat exchanger 673 to line 671a (80 ° C, 18 bar) . Refrigerant water flows from line 682 (30 ° C, 5 bar) to and through heat exchanger 673 and out of heat exchanger 673 through line 683 (34.2 ° C, 3.5 bar). Gaseous FT product flows through line 671a (80 ° C, 18 bar) to and through heat exchanger 674 and from heat exchanger 674 to and through line 671b (35 ° C, 18 bar) to three modes 67 5. A gas mixture flows out of the three mode separator 675 through line 676 (35 ° C, 18 bar). This gas mixture may be referred to as a residual gas FT. a liquid mixture flows out of the three-way separator 675 through line 677 (35 ° C, 18 bar). Such a liquid mixture may be referred to as processed condensate.

A liquid FT product flows from the three-way separator 675 through line 678 (35 ° C, 18 bar) to mixer 680 where it is combined with liquid FT product from line 672. The combined liquid FT product flows at from mixer 680 through line 681 (121 ° C, 18 bar) to fractionator 685 where the combined liquid FT product is fractionated. A light end product flows out of fractionator 685 through line 687 (121 ° C, 18 bar) to mixer 607. A liquid FT product flows from fractionator 685 through line 686 (121 ° C, 18 bar) for fractionator 690 where the liquid FT product is subjected to fractionation. Liquid FT product flows out of fractionator 690 through line 691 (121 ° C, 18 bar). This liquid FT product may be referred to as synthetic fuel. A bottom product flows out of fractionator 690 through line 692 (121 ° C, 18 bar) to mixer 607.

Table 1 Table 2 Table 3 Example 2 A Fischer-Tropsch reaction is performed in a microchannel reactor employing a fixed catalyst bed. The process is conducted at a high capacity (contact times in the order of approximately 290 to approximately 214 milliseconds) and provides high CO conversions (up to approximately 80%). The reactor is operated with a two-phase flow and shows little variation in pressure drop, with a standard deviation of less than 3% of the total pressure drop. High CO conversions and stable pressure drops are also associated with low CH4 selectivities, less than 15% for all cases, and less than 10% for most cases, coupled with higher C6 + hydrocarbon selectivity. than 75% for all cases and greater than 80% for most cases. The microchannel reactor has two process repeat units interspersed with three refrigerant repeat units. Process microchannels in process repeat units are in a cross flow orientation for refrigerant channels in refrigerant repeat units. This is shown in figure 29. The active reactor core has an area that is 15.2 cm by 15.2 cm. The overall reactor battery size is 25.4 cm by 19.1 cm by 6.17 cm. Refrigerant channels are formed of multiple wedges that include flow distribution characteristics. Process microchannels are formed of a copper waveform. This is shown in figure 30. This waveform has dimensions of 19.1 cm by 15.2 cm by 3.18 mm. The thickness of the waveform is 0.15 mm. The resulting microchannel reactor has 276 process microchannels formed in two layers. Each of the process microchannels has the average dimensions of 0.95 mm in width, 3.18 mm in height and 19.1 cm in length. Collectors and footers are connected to refrigerant channels and process microchannels to provide connection to larger external piping.

A catalyst bed is charged into the microchannel reactor as described below. The assembly is then enclosed in a process containment enclosure (PCS). The catalyst bed contains SiC particles and particles of an FT catalyst.

SiC particles are supplied by Atlantic Equipment Engineers from Bergen New Jersey, catalog number SI-312. A Malvern Hydro 2000 G light scattering particle distribution analyzer is used to measure the average volume diameter d (50) for SiC particles. SiC particles have an average diameter of 281 microns. The sealed bulk density (PABD) for SiC particles is 1.62 grams per cubic centimeter (g / cm3) in triplicate, and the empty fraction in PABD is 0.31. FT catalyst is provided by Oxford Catalyst Limited. This catalyst comprises cobalt and a support, the volume mediated particle size for the catalyst particles is 261 microns as determined using the Malvern Hydro 2000 G analyzer. Further catalyst screening shows that much of the catalyst mass between 210 and 250 microns higher in higher mesh sizes than lower mesh sizes. The PABD for the catalyst is 1.08 g / cm3 in triplicate. The empty fraction for PABD sealing is 0.362. Deionized water is added in 100 microliter aliquots using a pipette until water ruptures the surface. The wet catalyst is placed on a vibration table for 30 seconds at medium power to displace trapped air, settle the bed, and bring excess water to the surface. Excess water is removed using a pipette. The sample is allowed to air dry. The sample is then dried at 200 ° C for one hour at ambient pressure. Reactor volume is determined by the addition of methanol at room temperature. 151.5 cm3 of methanol fills the reactor waveform channels to the top.

A 100 ppi foam that has a thickness of 0.635 cm is inserted into the bottom of the reactor. The FT catalyst is added to the waveform and thickened using vibration from a rubber covered mallet. The total mass added is 143.22 grams. Full depth is measured on each waveform channel with measured length pins whose distance above the waveform aperture is measured with a graduated sheet and digital photography. The average difference in FT catalyst fill height and desired fill height of 17.145 cm is 0.467 cm below the desired level. The standard deviation for the filling height is 0.483 cm. The sealing density, considering the volume of the process waveform channels equal for the entire sealing height, is 1.068 g / cm3, or 1.1% lower than the 1.08 g / cm3 measured PABD. . The total volume of the catalyst is 134.1 cm3. The SiC layer is added to the top of the reactor and thickened to fill the reactor. A 100 ppi foam with a thickness of 0.635 cm is inserted into the top of the reactor.

The flow and composition of gas sin. Powered by the microchannel reactor is controlled using Brooks 5850E mass flow controllers. Hydrogen, carbon monoxide and nitrogen gases are supplied by Praxair, Matheson Tri-gas and Delile. These are powered through both the activated carbon and 13X molsieve manifolds. A sample orifice is located downstream of the mixing point to measure inlet gas composition. The gases are heated to> 300 ° C in a stainless steel microchannel heat exchanger, which is heated with nitrogen gas, before being fed to the microchannel reactor. Δ inlet pressure is measured using a pressure transmitter model Yokogawa EJA430A-H. The fixed process bed pressure drop is measured by a Yokogawa model EJA110A-H differential pressure transmitter. Inlet and outlet streams are analyzed using an Agilent 3000A RGA, (GC) refinery gas analyzer gas chromatography with extra channel for upper hydrocarbons. Residual gas samples are collected through a sample orifice located downstream of the reactor and upstream of the first product collection tank. The sample conditioner consists of a Neptune SC-316 sample chiller and a Swagelok 300 cm3 condensate collector. The flow through the sample conditioner is adjusted with a pressure regulator and needle valve and turned on only while in sample. Five to seven GC samples are collected for each gas measurement, with the first two discarded and the remainder mediated. Product flow is routed through three high pressure collection vessels, and cooled in stages to provide an approximate separation of lighter hydrocarbon products from heavier hydrocarbon products along with an aqueous phase. A first drum is heated with two Watlow band heaters at a local surface temperature of 120 ° C to 135 ° C. The heavier hydrocarbon and aqueous phase products are drained from the bottom and weighed. Gases exit the first drum at a temperature between 120 ° C and 140 ° C and are cooled to below 30 ° C on the first Sentry model 1253C57-EW6-H35X heat exchanger, which is cooled with Dow Dowfrost HD refrigerant. A second drum is at room temperature and is used to collect an aqueous phase and a clear liquid hydrocarbon phase. The remaining gases flow to a second model 1253C57-EW6-H35X heat exchanger, which is cooled to 10 ° C with propylene glycol refrigerant and then to a third collection tank, which collects less than 1% total condensate. After the third tank the waste gas arrives at a pressure control device for the process side. This device is a Kammer Model 030000 Globe Valve. The product is measured with an American Meter Company 100 liter / spin dry test meter equipped with a relay for signal transmission. A second waste gas sample hole is located downstream of the dry test meter for additional sampling. The reactor is heated and catalyst activation is performed under a hydrogen reducing atmosphere at 400 ° C and near ambient pressure. The reactor is then cooled and starting is initiated by increasing the pressure within the reactor to operating pressure, gradually turning on the refrigerant flow as well as the reactant feed mixture flow, and increasing the reactor temperature. The reagent feed mixture contains H2 and CO at a H2: CO molar ratio of 2: 1. The reagent feed mixture also contains 16.6 volume% N2. At a contact time of 290 ms, the reactor temperature is gradually raised to 210 ° C to achieve a constant state CO conversion greater than 70%. The standard deviation of the pressure drop is high as reaction conditions are established, and then it is lower as the system stabilizes. Pressure drop under selected time flow conditions illustrates stability over short and long periods: Around 1500 hours flow, the reactor operating conditions are adjusted to an input H2: CO ratio of 2.01, and 4% by volume of N2 in the feed at an inlet pressure of 24133.2 kPa (350 psig) and an inlet temperature of 222 ° C and a contact time of 214 ms. These conditions are maintained for 190 hours. Reactor performance shows a constant CO conversion of 68.8 ± 0.3%. The average selectivity for CH4 is 13.3 ± 0.1% and the selectivity for C6 + hydrocarbons is 74.8 ± 0.2%. Reactor pressure drop is constant as evidenced by a low standard deviation in pressure drop measurements. The average pressure drop during this operation is 12.1 kPa (1.75 ± 0.01 psi). The catalyst is reduced again around 1890 hours in flow and the reactor is restarted to the target condition with an input H2: CO ratio of 2.0, and 16.6% N2 in the feed. The inlet pressure is 241.2 kPa (350 psig), and the average inlet temperature is 211 ° C. Contact time is 290 ms. This set of reaction conditions is maintained for 420 hours. The CO conversion in the reactor is initially elevated around 75% and gradually stabilizes over the course of a few hundred hours at a constant value of 68.8 ± 0.3%. The average selectivity for CH4 is 8.9 ± 0.1% and for C6 + hydrocarbons is 77.8 ± 0.2%.

Corresponding to the CO conversion stabilization described above, the pressure drop initially increases and then stabilizes as the CO conversion drops to its final stable value. Reactor pressure drop during this operation remains constant as evidenced by the low standard deviation in pressure drop measurements. The mean pressure drop during this condition is 10.1 kPa (1.46 ± 0.4 psi).

Prior to data collection, a leak between the refrigerant side and the fixed bed (process) side is detected during normal pressure checking. From that moment on the refrigerant side is operated at a higher pressure than the process side so that any leakage would be liquid water or steam from the refrigerant side into the process side. Consequently a larger standard deviation for the process side pressure drop (two to four times) is seen here compared to the previous stroke.

Details of microchannel reactor performance throughout its operating life are summarized below.

Upon completion of the initial start-up, a target condition with H2: CO ratio of 2: 1 and 16.6% N2 in the feed at an average reactor temperature of 210 ° C and a contact time of 2 90 ms is reached which provides an average CO conversion of 71.7%. These process conditions are maintained from startup until around 1140 hours in flux. The CO conversion gradually stabilizes at an average value of approximately 71.7% and the corresponding average CH4 selectivity is 8.9%.

The contact time is then decreased to 214 ms and the reactor temperature gradually increased to 222 ° C to increase the CO conversion to its previous constant value. Under these conditions the average CO conversion is 71.9% with a selectivity of 77.2% for C6 + hydrocarbons. The corresponding steady state pressure drop is 12.7 kPa (1,843 ± 0.004 psi).

At around 1500 hours in flux the feed dilution is then decreased to 4% by volume and the reaction temperature is maintained at 222 ° C, and the average CO conversion is 68.8%. The corresponding average pressure drop is 12.1 kPa (1.75 psi).

The reactor conditions are then reverted to the initial starting condition by lowering the temperature to 210 ° C, increasing the N2 dilution to 16.6% and increasing the contact time to 290 ms. The average conversion of CO is 66.4%. This is approximately 5% lower than initial performance. This accentuates minimal time-out catalyst deactivation. The corresponding mean pressure drop of 10.1 kPa (1.46 ± 0.0.1 psi) is higher than 9.72 kPa (1.41 ± 0.01 psi) initially seen. This increase in pressure drop is commensurate with the decrease in conversion. The standard deviation of the pressure drop indicating the stability of flow development in the process microchannels remains virtually unchanged for 1880 hours in flux. The catalyst is reduced again by 1890 hours in flux with the catalyst spending half an hour above 400 ° C and approximately 2 hours above 390 ° C. A cross leak between the refrigerant and process sides is discovered after reduction. During the starting process the chiller pump fails causing an interlock shutdown event. When the reactor reaches the target temperature, the CO conversion is only 39% well below previous values. The catalyst is again reduced. The catalyst is then restarted to achieve a condition with a H2: C0 ratio of 2: 1 and 16.6% N2 in the feed at an average reactor temperature of 210 ° C and a contact time of 290 ms which corresponds to to the first constant condition after the initial departure. The initial CO conversion is slightly higher than the previous match but remains constant at a slightly lower value of 69.5%. The corresponding average pressure drop is 10.2 kPa (1.47 ± 0.04 psi). The standard deviation of the pressure drop increases compared to the original reactor startup. This also corresponds to the increase in a deactivation rate for the catalyst. The increase in standard deviation may be a result of the leak described above. The contact time is then decreased to 214 ms and the reactor temperature gradually increased to 223 ° C. This results in an average CO conversion of 70.4% and a C6 + selectivity of 76.0%. The H2: CO ratio is then changed to 1.5: 1 and the contact time increased to 255 ms. The reactor pressure is then increased to 2647.6 kPa (384 psig) and the reactor temperature gradually increased to 228 ° C leading to an average CO conversion of 60.9% at a 7.1% CH4 selectivity. Pressure drop decreases as CO conversion increases at higher pressure. The H2: CO ratio is changed to 1.5, and the dilution with N2 is increased to 40%. Reactor pressure is increased to 2895.8 kPa (420 psi) and reactor temperature increased to 232 ° C. As contact time is increased from 184 ms to 250 ms, CO conversion increases from 56.1% to 64.0%. The corresponding pressure drop decreases from 15.5 kPa (2.256 psi) to 10.65 kPa (1.545 psi). pressure drop decreases as contact time increases which reduces flow and increases CO conversion.

The reaction conditions are then reversed to a H2: C0 ratio of 2: 1 with 16.6% N2 in the feed. The average reactor temperature is 211 ° C and contact time is 290 ms. The CO conversion decreases to an average value of 59.6%. The average pressure drop is 10.48 kPa (1.52 ± 0.04 psi). This is higher than that at restart due to catalyst deactivation. The catalyst is then reduced again and restarted under the same reaction conditions as a 2: 1 H2: C0 ratio, 16.6% N2 at feed, average reactor temperature of 211 ° C and contact time of 290 ms. The CO conversion reaches a constant value of approximately 69.2% which is comparable to that obtained after the previous reduction. The corresponding average pressure drop is 10.34 kPa (1.50 ± 0.04 psi). The standard deviation of the pressure drop, which is indicative of flow stability, indicates a stable flow in the process microchannels that remains virtually unchanged for 1800 hours in flux.

Although the invention has been explained in connection with various embodiments, it should be understood that various modifications thereof may become apparent to those skilled in the art upon reading of this disclosure report. Therefore, it should be understood that the invention includes all such modifications which may be within the scope of the appended claims.

Claims (15)

Process for converting a carbonaceous material into a desired product, comprising one or more hydrocarbons or one or more alcohols, characterized in that it comprises: (A) gasifying the carbonaceous material at a temperature of at least about 700 ° C to form synthesis gas; and (B) flowing the synthesis gas into a microchannel reactor in contact with a catalyst to convert the synthesis gas into the desired product. Process according to Claim 1, characterized in that the carbonaceous material comprises coal, oil, biomass, solid waste, or a mixture of two or more thereof. Process according to Claim 1 or 2, characterized in that the carbonaceous material comprises municipal solid waste, hazardous waste, refuse-derived fuel, tires, refuse, sewage sludge, animal waste, petroleum coke, refuse, debris, agricultural waste, corn fodder, fast-growing grass, wood shavings, wood, grass clippings, building demolition materials, plastic material, cotton gin waste, landfill gas, biogas, natural gas, or a mixture of two or more thereof. Process according to any one of Claims 1 to 3, characterized in that the synthesis gas produced in step (A) comprises H2 and CO, and before step (B), an additional amount of H2 is added to the mixture. synthesis gas. Process according to any one of Claims 1 to 4, characterized in that the microchannel reactor comprises a plurality of process microchannels and a plurality of heat exchange channels, the catalyst being in the process microchannels, each channel. heat exchanger being in thermal contact with at least one process microchannel, at least one pipe for the flow of synthesis gas into the process microchannels, at least one pipe for the flow of product out of the process microchannels, at least at least one pipe for the flow of a heat exchange fluid into the heat exchange channels, and at least one pipe for the flow of heat exchange fluid out of the heat exchange channels. Process according to any one of Claims 1 to 5, characterized in that a plurality of microchannel reactors are positioned in a vessel, each microchannel reactor comprising a plurality of process microchannels and a plurality of exchange channels. heat, the catalyst being in the process microchannels, each heat exchange channel being in thermal contact with at least one process microchannel, the vessel being equipped with a pipe for the synthesis gas flow to the process microchannels, a pipe for the flow of the product from the process microchannels, a pipe for the flow of a heat exchange fluid to the heat exchange channels, and a pipe for the flow of the heat exchange fluid from the exchange channels of heat. Process according to any one of claims 1 to 6, characterized in that the catalyst used in step (B) is a Fischer-Tropsch catalyst, the reaction which is conducted in the microchannel reactor during step (B) is a Fischer-Tropsch reaction, and the desired product comprises one or more hydrocarbons. Process according to claim 7, characterized in that the Fischer-Tropsch catalyst comprises alumina supported Co, the Co charge being at least about 5% by weight. Process according to any one of claims 1 to 6, characterized in that the catalyst used in step (B) is an alcohol-forming catalyst, the reaction which is conducted in the microchannel reactor during step (B). It is an alcohol forming reaction, and the desired product comprises one or more alcohols. Process according to any one of claims 1 to 9, characterized in that the catalyst is in the form of particulate solids. Process according to any one of claims 1 to 10, characterized in that the catalyst is supported on a support having the configuration of a foam, felt, filler, fin, or a combination of two or more thereof. Process according to Claim 7, characterized in that the desired product is further processed using separation, fractionation, hydrocracking, hydroisomerization, wax removal, or a combination of two or more thereof. Process according to any one of claims 1 to 12, characterized in that water vapor is used as a heat exchange fluid in the microchannel reactor during step (B) and the carbonaceous material is gasified in the presence of a gasifying agent during step (A), the water vapor of step (B) being used as the gasifying agent during step (A). Process according to any one of claims 1 to 13, characterized in that the microchannel reactor comprises a plurality of process microchannels, the process microchannels being formed by positioning a waveform between flat sheets. Process according to any one of Claims 1 to 14, characterized in that the desired product produced in step (B) is a Fischer-Tropsch product, the process further comprising hydrocracking at least part of the Fischer product. -Tropsch in a microchannel reactor.