“[0004] Literature data (Table 1 and FIG. 1) were obtained at lower H 2/CO ratio (2:1) and longer contact time (3 sec or longer) in a fixed bed type reactor. Low H 2/CO (especially 2-2.5), long contact time, low temperature, and higher pressure favor Fischer-Tropsch synthesis. Selectivity to CH 4 is significantly increased by increasing H 2/CO ratio from 2 to 3. Increasing contact time also has a dramatic favorable effect on the catalyst performance. Although reference 3 in Table 1 shows satisfactory results, the experiment was conducted under the conditions where Fischer-Tropsch synthesis is favored (at least 3 sec residence time, and H 2/CO=2). In addition, the experiment of reference 3 was done using a powdered catalyst on an experimental scale that would be impractical commercially because of the pressure drop penalty imposed by powdered catalyst. Operating at higher temperature will enhance the conversion, however at the much higher expense of selectivity to CH 4. It is also noteworthy that contact time in commercial Fischer-Tropsch units is at least 10 sec. [0005] Hence, there is a need for a catalyst structure and method of Fischer-Tropsch synthesis that can achieve the same or higher conversion at shorter contact time, and/or at higher H 2/CO.”
“This property is defined by various testing conditions. For example, a preferred catalyst has a Fischer-Tropsch catalytic metal supported on a porous support; where the catalyst possesses catalytic activity such that [sic]. If the catalyst is placed in a tube inside an isothermal furnace and exposed to a feed stream consisting of a 3 to 1 ratio of hydrogen gas to carbon monoxide, at 250°C, at 6 atm, at a contact time less than 5 seconds and the product stream is collected and cooled to room temperature, the selectivity to methane is less than 25%, and the carbon monoxide conversion is greater than 25%. To check whether a catalyst meets a claimed activity property requires only a test at the specified conditions.”
“Advantages that may be provided by the invention include (i) at residence/contact times shorter than the prior art, higher conversions are achieved with no increase to methane selectivity; and (ii) as residence/contact times increase, conversion increases and methane selectivity decreases. Surprisingly, it has been found that carbon monoxide can be hydrogenated at short contact time to produce liquid fuels at good conversion levels, low methane selectivities and good production rates.”
“The porous support 100 may be a porous ceramic or a porous metal. Porous supports suitable for use in the present invention include carbides, nitrides, and composite materials. Prior to depositing the layers, the porous support preferably has a porosity of 30% to 99%, more preferably 60% to 98%, as measured by mercury porosimetry and an average pore size of from 1μm to 1000 μm as measured by optical and scanning electron microscopy. Preferred forms of porous supports are foams, felts, wads and combination, thereof. Foam is a structure with continuous walls defining pores throughout the structure. Felt is a structure of fibers with interstitial spaces there between. Wad is a structure of tangled strands, like steel wool. Less preferably, porous supports may also include other porous media such as pellets and honeycombs, provided that they have the aforementioned porosity and pore size characteristics. …”
“The interfacial layer 104 can be comprised of nitrides, carbides, sulfides, halides, metal oxides, carbon and combinations thereof. The interfacial layer provides high surface area and/or provides a desirable catalyst-support interaction for supported catalysts. The interfacial layer can be comprised of any material that is conventionally used as a catalyst support. Preferably, the interfacial layer is a metal oxide. …. The interfacial layer 104 may serve as a catalytically active layer without any further catalytically active material deposited thereon. Usually, however, the interfacial layer 104 is used in combination with catalytically active layer 106. …”
“The catalytically active material 106 (when present) can be deposited on the interfacial layer 104. Alternatively, a catalytically active material can be simultaneously deposited with the interfacial layer. The catalytically active layer (when present) is typically intimately dispersed on the interfacial layer. That the catalytically active layer is ‘disposed on’ or ‘deposited on’ the interfacial layer includes the conventional understanding that microscopic catalytically active particles are dispersed: on the support layer (i.e., interfacial layer) surface, in crevices in the support layer, and in open pores in the support layer. The present invention employs a Fischer-Tropsch catalytic metal in the catalytically active layer. … Catalytic metals in the present invention are preferably iron, cobalt, ruthenium, rhenium, osmium and combinations thereof. In addition to these catalyst metals, a promoter may be added. …”
“[0031] According to the present invention, a residence time less than 5 seconds can be achieved by: (a) providing a catalyst structure of a metal foam having a catalyst thereon; and (b) passing a feed stream having a mixture of hydrogen gas with carbon monoxide gas through the catalyst structure and heating the catalyst structure to at least 200°C, thereby obtaining a product stream of at least 25% conversion of carbon monoxide, and at most 25% selectivity toward methane. In another preferred method, the catalyst structure includes a buffer layer. 62. [0033]Residence and contact times have well-defined meanings in the art. Contact time is the total volume of the catalyst chambers divided by the total flowrate of inlet reactants assuming they are an ideal gas corrected to standard conditions (i.e., the volume of the catalyst chamber / F-total at STP where STP is 273K and 1 atm). The volume of the catalyst chambers includes the volume in immediate proximity and surrounding the catalyst zone. As an example, if one were to pack one quarter of the channels with powders, then the volume of the catalyst chamber would only include that region where gas can flow and where it can contact the catalyst, i.e. only one quarter of the total channel volume would be included in this calculation. The volume of dead space i.e., headers, footers, etc. is ignored in this calculation. Average residence time (also referred to as residence time) is the total volume of the catalyst chambers divided by the total flowrate of inlet reactants, corrected to the actual temperature and pressure of the reactants in the reactor (i.e., the volume of the catalyst chamber / F-total corrected to actual conditions). F-total at STP is the total volumetric flowrate of reactants (includes all reactants, and diluents if present). Inlet gases are typically metered with mass flow controllers set to standard conditions, i.e. the user presets the desired STP flowrate. F-total corrected to actual conditions = F-total-STP x (Temperature in K)/273 x 1 atm/(P actual in atm): this value is used to calculate the residence time or the ‘true time’ within a reactor. Most practitioners prefer to use contact time, because it is a convenient method to keep the time variable fixed while stepping through 10 degree C increments in reaction temperature etc. 63. [0034]Contact times less than 5 seconds may be accomplished with standard equipment but at the expense of significant energy to raise the space velocity of the reactants to overcome the pressure drop and poorer heat transfer leading to higher methane formation. Thus, the inventive method is preferably carried out in a reaction chamber in which the catalyst has a thickness of 1.5 cm or less and is touching or in close proximity (within 1 mm) of a reaction chamber wall, where the reaction chamber wall is in thermal contact with a heat exchanger. Heat transfer from the reaction chamber is preferably enhanced by addition of microchannels on at least one reaction chamber wall on the side of the reaction chamber wall opposite the catalyst structure. The catalyst preferably has contiguous and relatively large pores, such as in a foam, to 64. avoid large pressure drops. Preferably the pore size of the large pores in the catalyst is between 10 μm and 300 μm. 65. [0035] According to the present invention, carbon monoxide hydrogenation is conducted at a contact time of less then 5 seconds, more preferably, less than about 2 seconds and still more preferably between 0.1 and 1 seconds. At these contact times, good CO conversion and low methane selectivity can be obtained. Preferably, CO conversion is at least 25%, more preferably, at least 50%, and still more preferably, greater than 80%. Methane selectivity is preferably less than 25%, more preferably less than 20%, and still more preferably, between 15% and 5%. Additionally, these properties can be achieved with low pressure drops across the reaction chamber. …”
“1. A method of Fischer-Tropsch reaction, comprising the steps of: (a) providing a catalyst structure having a first porous structure with a first pore surface area and a first pore size of at least 0.1 μm; a porous interfacial layer with a second pore surface area and a second pore size less than said first pore size, said porous interfacial layer disposed upon said first pore surface area; and a Fischer-Tropsch catalyst selected from the group consisting of cobalt, ruthenium, iron, nickel, rhenium, osmium and combinations thereof placed upon said second pore surface area; and (b) passing a feed stream having a mixture of hydrogen gas with carbon monoxide gas through said catalyst structure and heating said catalyst structure to at least 200°C at an operating pressure, said feed stream having a residencecontact time within said catalyst structure less than 5 seconds, thereby obtaining a product stream of at least 25% conversion of carbon monoxide, and at most 25% selectivity toward methane. 2. The method as claimed in claim 1, wherein the contact time isless than about 2 seconds. 3. The method as claimed in claim 1, wherein the contact time isbetween 0.1 and 1 seconds. 4. 6. The method of any of claims 1-3 5 carried out in a reaction chamber in which the catalyst has a thickness of 1.5 cm or less and is touching or in close proximity of a reaction chamber wall.”
“1. A catalyst structure for Fischer-Tropsch, comprising said catalyst structure comprising a first porous structure with a first pore surface area and a first pore size of at least 0.1 μm; a buffer layer disposed on said porous structure; a porous interfacial layer with a second pore surface area and a second pore size less than said first pore size, said porous interfacial layer disposed upon buffer layer; and a Fischer-Tropsch catalyst selected from the group consisting of cobalt, ruthenium, iron, nickel, rhenium, osmium and combinations thereof placed upon said second pore surface area. said catalyst structure comprising a first porous structure with a first pore surface area and a first pore size of at least 0.1 μm; a buffer layer disposed on said porous structure; a porous interfacial layer with a second pore surface area and a second pore size less than said first pore size, said porous interfacial layer disposed upon buffer layer; and a Fischer-Tropsch catalyst selected from the group consisting of cobalt, ruthenium, iron, nickel, rhenium, osmium and combinations thereof placed upon said second pore surface area. 7. The catalyst structure as recited in claim 1, wherein said buffer layer is selected from the group consisting of Al 2O 3, TiO 2, SiO 2 and ZrO 2 and combinations thereof. 9. A method of Fischer-Tropsch reaction, comprising the steps of: (a) providing a catalyst structure comprising a porous support with a first pore surface area and a first pore size of at least 0.1 μm; a buffer layer disposed on said porous support a porous interfacial layer with a second pore surface area and a second pore size less than said first pore size, said porous interfacial layer disposed upon said buffer layer; and a Fischer-Tropsch catalyst selected from the group consisting of cobalt, ruthenium, iron, nickel, rhenium, osmium and combinations thereof placed upon said second pore surface area; and (b) passing a feed stream having a mixture of hydrogen gas with carbon monoxide gas through said catalyst structure and heating said catalyst structure to at least 200°C at an operating pressure, said feed stream having a residencecontact time within said catalyst structure less than 5 seconds, thereby obtaining a product stream of at least 25% conversion of carbon monoxide, and at most 25% selectivity toward methane. 10. The method as claimed in claim 9, wherein the contact time isless than about 2 seconds. 11. The method as claimed in claim 9, wherein the contact time isbetween 0.1 and 1 seconds. 14. 16. A method of making a Fischer-Tropsch catalyst structure, comprising the steps of: providing a catalyst structure comprising a porous support with a first pore surface area and a first pore size of at least 0.1 flm; depositing a buffer layer on said porous support, depositing a porous interfacial layer with a second pore surface area and a second pore size less than said first pore size, upon said buffer layer, placing a Fischer-Tropsch catalyst selected from the group consisting of cobalt ruthenium, iron, rhenium, osmium and combinations thereof upon said second pore surface area.”
“Linguistic errors, errors of transcription and mistakes in any document filed with the European Patent Office may be corrected on request. However, if the request for such correction concerns a description, claims or drawings, the correction must be obvious in the sense that it is immediately evident that nothing else would have been intended than what is offered by the correction.”
“With regard to a correction under Rule 88, second sentence, EPC it follows that the parts of a European patent application or of a European patent relating to the disclosure must, either on the date of filing or following an amendment under Article 123 EPC, contain such an obvious error that a skilled person is in no doubt that this information is not correct and—considered objectively—cannot be meant to read as such. If, on the other hand, it is doubtful whether any information at all is incorrect, then a correction is ruled out. The same applies if incorrect information only becomes apparent in the light of the proposed correction. The parts of a European patent application as filed which relate to the disclosure must further allow a skilled person—using the common general knowledge on the date of filing—directly and unequivocally to ascertain the precise content of the information the person making the request actually meant to give, instead of the incorrect particulars, on the date of filing or when making an amendment under Article 123 EPC, so that, for said skilled person, ‘it is immediately evident that nothing else would have been intended than what is offered as the correction’ (Rule 88, second sentence, EPC). However, if there is any doubt that nothing else would have been intended than what is offered as the correction, a correction cannot be made.”
“The corrected information merely expresses what a skilled person, using common general knowledge, would already derive on the date of filing from the parts of a European patent application, seen as a whole, relating to the disclosure.”
“For references that contained results for multiple experimental conditions, the run which best matched our conversion, selectivity and/or conditions was chosen for comparison of contact time”
“Broadly stated, the invention contemplates rendering a metal which normally would be unsuitable as the substrate for a catalyst to be used at high temperature (e.g. above 1200o F.), suitable for such use by first coating the metal with a thin high temperature oxidation resistant layer, as defined below; prior to conventional washcoating with alumina or other material and application of the catalytically active material, e.g. platinum group metal.”
“After application of the oxidation resistant coating, a conventional high surface area refractory oxide washcoat, preferably alumina, is applied in the usual fashion followed by drying and calcining and application of the platinum group metal or metals, all as conventionally employed in the preparation of exhaust gas catalysts …”
“The Fecralloy substrate had been heat treated at high temperature to form an aluminum oxide ‘keying’ surface. Catalyst B was completed by dipping the heat treated Fecralloy cylinder in a conventional alumina washcoat, followed by drying, calcining and then depositing platinum group metals (2 parts Pt, 1 part Pd) on the washcoat in conventional fashion.”
“Various modifications may be made in the invention as described in the foregoing. Thus, while the catalyst has been described in connection with the treatment of exhaust gas for the control of hydrocarbon and carbon monoxide pollutants, the catalyst may be used for other purposes. For example, the present catalyst may be used in processes involving catalytic (flame less) combustion, ammonia oxidation, high temperature catalytic oxidations other than automobile exhaust control (e.g. fume and/or odor abatement), high temperature catalytic hydrogenation including methanation, Fischer Tropsch reaction, coal liquefaction, nitric oxide abatement, and the like. More specifically, methanation and Fischer Tropsch reactions can be carried out by contacting CO and H2 gas, with or without added steam, with the present catalyst…. ”
“It is an object of the present invention to provide a reaction system for an F-T synthesis which has high mass transfer characteristics at the catalyst and in which heat transfer is not a significantly limiting factor, without the drawback of a difficult catalyst separation.”
“Accordingly, the invention is directed to the use of a monolithic catalyst to conduct a Fischer-Tropsch synthesis, in which the monolith comprises a solid body defining a series of discrete and continuous channels extending from one end of the body to the other, the walls of the channels consisting of or containing a Fischer-Tropsch catalyst. The invention also provides a method of conducting a FischerTropsch synthesis reaction which comprises: passing synthesis gas comprising H 2 and CO through discrete and continuous channels in a monolithic catalyst the walls of the channels consisting of or containing a Fischer-Tropsch catalyst; removing the liquid product from the monolith; and removing heat produced in the reaction in the liquid product. Preferably heat from the reaction is removed from the liquid product stream outside the reactor and a portion of the liquid product stream is recycled to the reactor. Unreacted synthesis gas may be recycled from the reactor, for example to the synthesis gas production unit. Preferably, the synthesis gas feed and the liquid product flow co-currently. Preferably the synthesis gas feed and liquid product travel along the channels in a slug flow or Taylor Flow regime. Taylor Flow of a gas and liquid in a channel is defined as periodic cylindrical gas bubbles in the liquid having almost the same diameter as the channel and without entrained gas bubbles between successive cylindrical bubbles. Preferably, the flow is downwards.”
“In the proposed monolith reactor design, cooling is performed by direct heat removal by the production stream (preferably the heavy FT products) which may circulate. The circulating liquid can then be cooled in an external heat exchanger. If necessary, the cooling can be carried out in stages by dividing the reactor in different sections with separate cooling circuits. … In a monolithic reactor operating in two-phase flow (gas + liquid), particularly under Taylor Flow conditions, mass transfer occurs mainly in the thin film between the cylindrical bubbles and the channel walls containing the catalytic material. This mode of flow occurs over a wide range of gas and liquid superficial velocities. … … a monolith reactor will show negligible backmixing, i.e. near plug-flow. The narrow channels of a monolith and the Taylor-flow mode of operation in two-phase flow results in almost perfect plug-flow. Scale-up is therefore simple since the entire reactor can be described by a single channel.”
“In many monolith applications, the thermal stability of the material and the ability to withstand rapid temperature variations are both of great importance. Therefore, the channel structure of a monolith usually consists of a low-surface area ceramic material. The surface area can be increased by depositing a high surface area material (like γ-Al 2O 3) e. g. by the so-called washcoating technique. Catalytically active materials can then be incorporated into the washcoat by known techniques, like impregnation, precipitation, ion-exchange, vapour deposition etc. Alternatively, the low surface area base material can be washcoated with the catalytic material itself. Thus in one preferred form, the monolithic catalyst comprises an inactive substrate with a relatively low specific surface area, and, lining the channels, a relatively high specific area catalyst support impregnated with a catalytically active material. Preferably the catalyst support material and the active material are deposited simultaneously on the walls of the channels. Alternatively, the catalyst support material is first deposited on the walls of the channels and is subsequently impregnated with the active material. The inactive substrate may be a ceramic material or a metal. Examples of suitable materials are set out in Table 1 (taken from ‘Monolithic Catalysts for Nonautomobile Applications’ by S Irandoust and B Andersson, Catal. Rev. Sci. Eng., 30(3), 1988). 134. A monolith-based FT catalyst can thus be made by impregnation (or by other techniques) of an active FT-metal (Co,Fe,Ru,Ni) and suitable promoters on a high-surface area washcoated monolith or by washcoating the finished FTcatalyst onto the low-surface area monolith. 135. In slower reactions like the Fischer Tropsch synthesis, thermal stability is not a critical factor. In such cases, monoliths can be made directly from high surface area materials, for example gamma-Al 2O 3, SiO 2, TiO 2 or zeolites. The catalytic material (e.g. cobalt, iron ruthenium or nickel in the case of FTsynthesis) and optionally suitable promoters can then be incorporated into the total volume of the monolith (by any of the known techniques), thus increasing the catalyst loading of' the reactor compared to the washcoat method. Alternatively, the monolith can be produced directly from the FT-catalyst. Production of high surface area monoliths is usually achieved by extrusion.”
“In an alternative construction shown in Figure 2, the monolith is a cross-flow design. In this case, the gases are arranged to travel along one series of channels 24 and the cooling liquid along the transverse channels 25 which alternate vertically with the gas channels.”
“Approximately 10 cm long cylindrical low surface area cordierite monoliths (Celcor (reg. trademark) from Corning) with a diameter of about 0.9 cm were used as base materials.”
“It is shown that the washcoated monolith catalysts (D&E) are as active as the conventional (powder) catalysts (A-C). The application of two washcoat layers (cat. E) on the cordierite base does not influence the catalyst performance compared to the single layer monolith (cat. D). The high-surface area monolith catalyst (F) contained more cobalt per volume of reactor than the other catalysts and it was found that 195°C was the maximum acceptable reactor temperature due to heat removal limitations in a gas-phase reactor. These limitations will not be present in a monolith reactor operating with liquid coolant. After correcting for the temperature difference, it is evident that the high-surface area monolith is at least as active per unit mass of cobalt as the conventional (powder) catalysts and also similar to the crushed high-surface area monolith catalyst (G). The high C5+ selectivity indicates that hot-spots were not present during reaction.”
“Difference in thermal conductivity is of particular importance. Metallic monoliths gave about two orders of magnitude higher thermal conductivity than ceramic monoliths. Ceramic monoliths are almost adiabatic, while radial heat transfer in metallic monoliths is of the same magnitude as in packed beds.”
“According to Pratt and Cairns [11], who studied the use of metal catalysts on metallic substrates, the use of metal substrates is favourable for applications involving high-flow, high-temperature environments.”
“Metallic monoliths are made to withstand oxidating atmosphere at high temperatures. … Aluminum containing ferritic steels produce [sic] layer of aluminium oxide which makes the alloy operative up to 1500 K [11]. Metallic monoliths are usually made of the alloys Kanthal and Fecralloy (Table 6). Fecralloy contains iron, chromium, aluminum and a small percentage of ytterium.”