巴西专利BR112013024588B1 PROCESS FOR THE CONVERSION OF SYNTHESIS GAS TO UPPER HYDROCARBONS

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专利摘要:
fischer-tropsch process in a radial reactor. the present invention relates to a process for converting synthesis gas to larger hydrocarbons by contacting a gaseous stream comprising synthesis gas with a particulate fischer-tropsch catalyst, said process being carried out in a tubular reactor having an inlet and an outlet, said outlet being located downstream of the inlet, said reactor comprising one or more tubes having located in them one or more carriers for said particulate catalyst and cooling means in contact with said tubes; wherein said catalyst carrier comprises: an annular container for holding catalyst in use, said container having a perforated inner wall defining a tube, a perforated outer wall, a top surface closing the annular container and a bottom surface closing the container cancel; a surface closing the bottom of said tube formed by the inner wall of the annular container; a skirt extending upwardly from the perforated outer wall of the annular container from a position on or near the bottom surface of said container to a position below the location of a seal; and a seal extends from the container a distance that extends beyond an outer surface of the skirt; said process comprising: (a) introducing the gaseous reagents through the inlet; (b) passing said reagents down through at least one said tube to the upper surface of, or the first catalyst carrier where they pass through the passage defined by the perforated inner wall of the container before passing radially through the catalyst bed to the perforated external wall; (c) allowing the reaction to take place as the synthesis gas puts the catalyst in contact; (d) pass unreacted reagent and product out of the container through the perforated outer wall, and then upwards between the inner surface of the skirt and the outer wall of the annular container until they reach the seal where they are directed over the skirt end and caused to flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs; (e) repeat steps (b) to (d) on any subsequent catalyst carrier; and (f) removing product from the outlet.
公开号:BR112013024588B1
申请号:R112013024588-3
申请日:2012-02-06
公开日:2020-09-08
发明作者:Timothy Douglas Gamlin
申请人:Johnson Matthey Davy Technologies Limited；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a process for converting carbon monoxide and hydrogen (synthesis gas) to liquid hydrocarbon products in the presence of a Fischer-Tropsch catalyst.
[0002] [002] In the Fischer-Tropsch synthesis reaction a gas mixture of carbon monoxide and hydrogen is reacted in the presence of a catalyst to provide a mixture of hydrocarbons having a relatively wide molecular weight distribution. The product is predominantly a straight chain, saturated hydrocarbons that typically have a chain length of more than 2 carbon atoms, for example, more than 5 carbon atoms.
[0003] [003] The ability to build hydrocarbons from synthesis gas is an attractive alternative in the production of hydrocarbons by cracking oil. This approach to hydrocarbons has increased as oil production has struggled to keep up with the growing demand for high quality fuel and further increased as oil reserves have decreased and those reserves have become richer in carbon.
[0004] [004] It is therefore desirable to optimize the Fischer-Tropsch process. Several approaches have been taken and have been of the catalyst. One of the main issues with the process is that the heat involved in the reaction is being very substantial, for example, approximately twice that produced by the reaction to produce methanol during the equivalent conversion of carbon oxides.
[0005] [005] One approach to maintaining the high heat involved is to carry out the reaction in a fixed bed reactor. In this arrangement, catalyst pellets are loaded into tubes in an axial reactor. Cooling medium, such as vaporizing water, is provided around the tubes. Reagent gases are then passed through the tubes where they come into contact with the catalyst and the Fischer-Tropsch reaction occurs. The heat involved is transferred through the pipe wall to the surrounding cooling medium. In view of the need to control heat inside the tube, the size of the tubes is limited to allow heat to pass easily from the center of the tubes to the walls where the heat exchange occurs. Generally, therefore, the tubes have a diameter of less than about 40 mm to ensure the necessary level of heat transfer and to prevent the catalyst located to the center of the tube from overheating and thermal disruption occurs. The small size of the tubes contributes to the high construction cost of these reactors.
[0006] [006] Even in the small tube size, the catalyst particles had to be relatively small in order to ensure reasonable mixing and heat transfer. In addition, careful selection of conditions, such as surface velocity and hourly space velocity of gas, must be performed in order to maintain the necessary heat transfer and manage the conversion of reactant gases into a reasonable overall pressure drop.
[0007] [007] When approaching tubes the upper size limit has been proposed to use larger catalyst particle sizes and to incorporate gas and / or liquid recycling to intensify the cooling of the tube. However, this approach has some disadvantages since there is significant resistance to mass transfer in Fischer-Tropsch catalyst particles where the lightest reagents and products have to be transported through the wax. This leads to selectivity by increasing unwanted lighter products and generating even more unwanted heat at the center of the particle.
[0008] [008] In an attempt to solve these so-called "eggshell" catalysts, it has been proposed that the surface of a support is impregnated. However, these catalysts provide less active catalyst per unit volume of the reactor and therefore reduce the productivity, and therefore the economy, of the process.
[0009] [009] It has also been proposed to reduce carbon monoxide to hydrogen ratio in the reactant gas to optimize the mass transfer of carbon monoxide in the center of the catalyst particle. Although this does not improve the selectivity of the catalyst, reaction kinetics are delayed which can lead to various problems, such as carbide formation, which must be removed periodically.
[0010] [0010] An additional problem is that the reduced catalyst cannot generally be used in the fixed bed reactors so that the equipment has to be placed during the initial reduction to allow during regeneration of the catalyst if necessary. In some cases, this requires that the design conditions of the reaction vessel are considerably in excess of normal operating conditions thereby increasing capital costs.
[0011] [0011] An alternative approach is to carry out the reaction in a bubble and mud reactor. In this arrangement, small catalyst particles, such as those of 150 pm or less, are suspended in the hydrocarbon product and are agitated by injecting reaction gas into the bottom of the reactor. The gas becomes highly dispersed through the reactor and therefore, in theory, the mass transfer area from the gas to the catalyst is very large. In addition, as the diameter of the catalyst is low, the mass transfer and heat transfer resistances within the catalyst particle are also low. Since the surface area of the catalyst is relatively large, the heat transfer from the catalyst particle to the fluid is high so that the particles can be maintained in addressing the fluid temperature conditions. The high evolution of heat in the reaction can be managed with internal and external coils, in which water is vaporized. So in theory, carrying out the process in a bubble and mud reactor offers several advantages.
[0012] [0012] However, in practice there may be significant mass transfer resistances in bubble and mud reactors such that high partial pressures of water can be experienced within the catalyst particles. Workers reported problems such as catalyst oxidation and damage to the catalyst due to the hydrothermal attack of the catalyst support structures. In addition, catalyst friction can be a significant problem that can lead to product purity and catalyst loss issues caused by the difficulty of arranging proper separation of much smaller particles in the product.
[0013] [0013] Other Fischer-Tropsch catalysts based on cobalt may be susceptible to contamination by still very low levels of impurities, such as sulfur species. This is a particular issue in bubble and mud reactors since, if the synthesis gas includes poisons, the entire catalyst inside the reactor will be exposed to contaminants whereas in fixed bed reactors, the first catalyst can be exposed to contaminants which tends to act as a protective bed for subsequent catalyst.
[0014] [0014] It will be understood that bubble and slurry reactors provide a challenging environment for catalysts and therefore long catalyst load lives are difficult to achieve leading to frequent or continuous removal of spent catalyst and replacement with fresh catalyst load resulting in reduced average production per catalyst unit and increases the cost of operating the system.
[0015] [0015] In addition, in order to optimize the operation of the bubble and mud reactor, it has to be relatively high in order to achieve the necessary level of agitation and mass transfer. Sufficient liquid must be contained in the reactor to accommodate the catalyst in concentrations in the region of 20 to 30 weight percent which results in a large volume of liquid contained. When these reactors are in operation, the gas kept inside the slurry is also significant. This requires extra reactor capacity to accommodate the mud bed in the burned state. To accommodate this, the reactors are generally in the order of 60 m in height. Such large reactors are heavy, which become expensive and difficult to implement. If the installation site is not close to a substantial channel, transport issues such as a large reactor become critical.
[0016] [0016] More recently, it has been suggested that a reactor called a microchannel can be used to improve the Fischer-Tropsch reaction system by intensifying the process. The key to this approach is to carry out the reaction in narrow channels between the plates of a reactor raising the flow. In this arrangement, high heat transfer coefficients and high specific productivity can be achieved. This approach also allows for mass transfer resistances to be minimized using highly active catalysts on extended surfaces.
[0017] [0017] These microchannel reactors are made by connecting plates to form passages during the flow of the cooling medium. These reactors had to be manufactured by specialists and had to be contained in the containment vessels. Thus, the capital cost of these provisions is substantial. An additional problem is that there is a limit on the size at which modular units can be manufactured and the reactors surprisingly had a high specific weight per unit of production making them expensive to manufacture.
[0018] [0018] As high specific activity is required from catalysts used in microchannel reactors, they tend to operate at higher temperatures and produce products at the lighter end of the hydrocarbon chain spectrum.
[0019] [0019] An additional problem associated with microchannel reactors concerns the risk of poisoning, to which as indicated above, Fischer-Tropsch catalysts are particularly susceptible. In a microchannel reactor, the relative amount of catalyst used is low and therefore, if poisoning occurs, a significant reduction in performance will also be observed. If the catalyst becomes deactivated, the developers stated that it is necessary to return the reactor module to the factory to have the catalyst removed and replaced, resulting in high cost and less expensive reactors with significant downtime are kept as spare parts. Therefore, microchannel reactors are generally only used in small capacity situations such as in works called "flaring" where realization and costs are less than the problems associated with eliminating inconvenient gas.
[0020] [0020] An alternative arrangement is discussed in WO 2010/069486, in which a number of adiabatic reactors are arranged in series. Since the described temperature rises is substantial, this arrangement cannot be expected to offer good performance with Fischer-Tropsch catalysts. In particular, high temperatures could be expected to cause rapid catalyst deactivation. In addition, at a reasonable total conversion, high methane would be expected.
[0021] [0021] Therefore, it must be understood that while the different approaches carried out in Fischer-Tropsch reactions, each one offers some advantages, they also have their own disadvantages. There is therefore still a need to provide an improved Fischer-Tropsch process that overcomes one or more of the problems in the prior art provisions.
[0022] (a) introduzir os reagentes gasosos através da entrada; (b) passar os referidos reagentes para baixo através de pelo menos o referido tubo à superfície superior de, ou o primeiro portador de catalisador onde os mesmos passam na passagem definida pela parede interna perfurada do recipiente antes de radialmente passar através do leito do catalisador para a parede externa perfurada; (c) permitir que a reação ocorra como o gás de síntese coloca em contato o catalisador; (d) passar reagente não-reagido e produto fora do recipiente através da parede externa perfurada e, em seguida para cima entre a superfície interna da saia e a parede externa do recipiente anular até que os mesmos alcancem a vedação onde os mesmos são direcionados sobre a extremidade da saia e causados para fluir para baixo entre a superfície externa da saia e a superfície interna do tubo reator onde transferência de calor ocorre; (e) repetir as etapas de (b) a (d) em qualquer portador de catalisador subsequente; e (f) remover produto a partir da saída. [0022] In accordance with the present invention, a process is provided for converting synthesis gas to larger hydrocarbons by contacting a gaseous stream comprising synthesis gas with a particulate Fischer-Tropsch catalyst, said process being carried out in a tubular reactor having an inlet and an outlet, said outlet being located downstream of the inlet, said reactor comprising one or more tubes having located in them one or more carriers for said particulate catalyst and cooling means in contact with at least said tube; wherein said catalyst carrier comprises: an annular container for holding catalyst, said container having a perforated inner wall defining a tube, a perforated outer wall, a top surface closing the annular container and a lower surface closing the annular container; a surface closing the bottom of said tube formed by the inner wall of the annular container; a skirt extending upwardly from the perforated outer wall of the annular container from a position on or near the bottom surface of said container to a position below the location of a seal; and a seal located at or near the top surface and extending from a container a distance that extends beyond an outer surface of the skirt; the referred process that comprises: (a) introducing the gaseous reagents through the inlet; (b) passing said reagents down through at least said tube to the upper surface of, or the first catalyst carrier where they pass in the passage defined by the perforated inner wall of the container before radially passing through the catalyst bed to the perforated external wall; (c) allowing the reaction to take place as the synthesis gas puts the catalyst in contact; (d) pass unreacted reagent and product out of the container through the perforated outer wall, and then upwards between the inner surface of the skirt and the outer wall of the annular container until they reach the seal where they are directed over the end of the skirt and caused to flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs; (e) repeat steps (b) to (d) on any subsequent catalyst carrier; and (f) removing product from the outlet.
[0023] [0023] The catalyst carrier is described in detail in POT / GB2010 / 001931 deposited on 19 October 2012, which is incorporated herein by reference.
[0024] [0024] For the avoidance of doubt, any discussion of orientation, for example, terms such as, up, down, bottom, and the like had for ease of reference discussed with respect to the orientation of the catalyst carrier as illustrated in the attached drawings. However, where the tubes, and therefore the catalyst carrier, are used in an alternate orientation, the terms must be constructed properly.
[0025] [0025] The catalyst container will generally be dimensioned such that it is smaller than the internal dimension of the reactor tube in which it is placed. The seal is dimensioned such that it interacts with the inner wall of the reactor tube when the catalyst carrier of the present invention is in position within the tube. The seal needs not to be provided perfect as it is sufficiently effective to cause most of the gas flow to pass through the carrier.
[0026] [0026] Generally, a plurality of catalyst carriers will be stacked inside the reactor tube. In this arrangement, the reagents / products flow down between the outer surface of the skirt of a first carrier and the inner surface of the reactor tube until they bring the upper surface and the seal of a second carrier into contact and are directed downwards into the second carrier tube defined by the perforated inner wall of its annular container. The trajectory described above is then repeated.
[0027] [0027] The catalyst carrier can be formed from any suitable material. Such material should generally be selected to withstand the reactor's operating conditions. Generally, the catalyst carrier must be manufactured from carbon steel, aluminum, stainless steel, other alloys or any material capable of withstanding the reaction conditions.
[0028] [0028] The wall of the annular container can be of any suitable thickness. Suitable thickness should be on the order of about 0.1 mm to about 1.0 mm, preferably on the order of about 0.3 mm to about 0.5 mm.
[0029] [0029] The size of the perforations in the inner and outer walls of the annular container should be selected as to allow uniform flow of reagents and products through the catalyst while keeping the catalyst inside the container. It should therefore be understood that its size will depend on the size of the catalyst particles being used. In an alternative arrangement, the perforations can be sized such that they are larger, but have a filter mesh that covers the perforations to ensure that the catalyst is kept within the annular container. This allows for large perforations to be used, which will facilitate the free movement of reagents without a significant loss of pressure.
[0030] [0030] It should be understood that the perforations can be of any suitable configuration. In fact, where a wall is described as all perforated it is necessary that there are means to allow reagents and products to pass through the walls. These can be small openings of any configuration, they can be grooves, they can be formed by a screening wire or any other means of creating a permeable or porous surface.
[0031] [0031] Although the top surface closing the annular container should generally be located at the top edge of or each wall of the annular container, it may be desirable to locate the top surface below the top edge such that a portion of the top edge of the outer wall forms a board. Similarly, the bottom surface can be located at the bottom edge of, or each, wall of the annular container or it may be desirable to locate the bottom surface such that it is above the bottom edge of the wall of the annular container such that the wall forms an edge.
[0032] [0032] The bottom surface of the circular crown and the surface closing the bottom of the tube can be formed as a single unit or the same can be two separate pieces connected together. The two surfaces can be coplanar, but in a preferred arrangement, they are on different planes. In one arrangement, the surface closing the bottom of the tube is in a lower plane than the bottom surface of the annular container. This serves to assist in locating a carrier to a carrier arranged below when a plurality of containers are to be used. It should be understood that in an alternative arrangement, the surface closing the bottom of the tube may be on a higher plane than the bottom surface of the annular container.
[0033] [0033] While the bottom surface should generally be solid, it may include one or more leakage holes. Where one or more leakage holes are present, they can be covered by a filter mesh. Similarly, a leakage hole, optionally covered with a filter mesh, can be present on the surface closing the bottom of the tube. Where the carrier is to be used in a non-vertical orientation, the leak hole, where present, will be located in an alternate position, that is, one that is the lowest point in the carrier when in use.
[0034] [0034] One or more spacer means may extend downwardly from the bottom surface of the annular container. The, or each, of the spacer means can be formed as separate components or they can be formed by depressions in the lower surface. Where these spacer media are present, they assist by providing a clear path for reagents and products to flow between the lower surface of the first carrier and the top surface of a second lower carrier in use. The spacer can be on the order of about 4 mm to about 15 mm, or about 6 mm deep. Alternatively, or in addition, spacer means may be present on the top surface.
[0035] [0035] The top surface closing the annular container may include in its upper surface means to locate the container against a catalyst carrier stacked above the container in use. The means for locating the container can be of any suitable arrangement. In one arrangement, it comprises a vertical collar having openings in the spaces there to allow during the entry of reagents.
[0036] [0036] The skirt that extends upwards can be smooth or it can be in shape. Any suitable form can be used. Suitable shapes include pleats, ripples and the like. The pleats, ripples and the like will generally be longitudinally arranged along the length of the carrier. The shape of the vertical skirt increases the surface area of the skirt and assists with the insertion of the catalyst carrier in the reaction tube as it will allow any surface roughness on the inner surface of the reactor tube or differences in tolerances in tubes to be accommodated .
[0037] [0037] Where the skirt that extends upwards is in shape, it will generally be flattened to a smooth configuration through the point where it is connected to the annular container to allow a gas seal to be formed with the annular container . The vertical skirt will generally be connected to the outer wall of the annular container at or near the base of the same. Where the skirt is connected at a point above the bottom of the wall, the wall will be free of punctures in the area below the connection point. The vertical skirt can be flexible.
[0038] [0038] Generally, the vertical skirt will stop at about 0.5 cm to about 1.5 cm, preferably about 1 cm, short of the top surface of the annular container.
[0039] [0039] Without wishing to be limited by any theory, it is believed that the vertical skirt serves to collect the reagents / products from the perforated outer wall of the annular container and direct them through the shapes to the top of the catalyst carrier collecting more reagents / products leaving the outer wall of the annular container as they move upwards. As described above, reagents / products are then directed downwards between the tube wall and the outside of the vertical skirt. By this method, the heat transfer reinforces down the entire length of the carrier, but as the heat exchange is separated from the catalyst, hotter or cooler as an appropriate heat exchange fluid can be used without abruptly cooling the reaction on the tube wall and at the same time ensuring that the temperature of the catalyst to the center of the carrier is properly maintained.
[0040] [0040] The seal can be formed in any suitable way. However, it will generally be sufficiently compressible to accommodate the smaller diameter of the reactor tube. The seal will generally be a flexible, sliding seal. In one arrangement, an O-ring can be used. A compressible recovery ring or a ring having a high expansion coefficient could be used. The seal can be formed from any suitable material provided that can withstand reaction conditions. In one arrangement, it can be a deformable flange that extends from the carrier. The flange can be sized to be larger than the inner diameter of the tube such that as the container is inserted into the tube it is deformed to fit inside and interact with the tube.
[0041] [0041] In the present invention, the annular space between the outer surface of the catalyst container and the inner surface of the tube wall is small, generally on the order of about 3 mm to about 10 mm. This narrow opening allows a heat transfer coefficient to be achieved such that an acceptable temperature difference of the order of about 10 ° C to about 40 ° C between the cooled outlet gas and the cooler to be achieved.
[0042] [0042] The size of the circular crown between the skirt and the catalyst wall and the skirt and the pipe wall will generally be selected to accommodate the required gas flow while maintaining high heat transfer and low pressure drop. Therefore, the process of the present invention may include the additional step of selecting the appropriate size of the circular crown to meet these criteria.
[0043] [0043] The process of the present invention relatively allows large reactor tubes to be used. In particular, tubes having diameters in the region of about 75 mm to about 130 mm or even about 150 mm can be used compared to diameters of less than about 40 mm used in conventional systems. The large diameter tubes will allow capacity in the region of 1192.4 m3 / day (10,000 US bbl / day) to be achieved in a single reactor of less than 6 m in diameter and less than 700 tons in weight.
[0044] [0044] As discussed above, the highly exothermic nature of the Fischer-Tropsch reaction is a major factor in the design of a reactor in which the reaction can be carried out. The use of the catalyst carrier in the process of the present invention, allows tubes that comprise a plurality of catalyst carriers to become, in reality, a plurality of inter-cooling adiabatic reactors.
[0045] [0045] Any suitable catalyst can be used in the process of the present invention. Powdered, foamed, structured forms or other suitable forms can be used.
[0046] [0046] A benefit of the process of the present invention is that the carrier allows the development of small diameter Fischer-Tropsch catalysts to be used as those having diameters from about 100 pm to about 1 mm. Since these are used in a fixed bed, the mass transfer resistances can be greatly reduced over the prior art provisions. This will lead to the improved selectivity of the required products, particularly those having a five-carbon chain length of five or more.
[0047] [0047] Additionally, as these small catalysts have a high surface area and are located in the direct flow of the reactant gas, they are maintained at a temperature that is very similar to that of the flow gas. This will reduce the tendency for by-product formation.
[0048] [0048] In an alternative arrangement, a monolith catalyst can be used. In this arrangement, the structure of the catalyst container can be modified. Full details of a catalyst container suitable for use with a monolith catalyst are described in GB patent application No. 1105691.8 filed on April 4, 2011, the contents of which are incorporated herein by reference.
[0049] (a) introduzir os reagentes gasosos através da entrada; (b) passar os referidos reagentes para baixo através de pelo menos um referido tubo à superfície superior de, ou o primeiro catalisador de monólito onde os mesmos passam através do catalisador de monólito; (c) permitir que a reação ocorra como o gás de síntese coloca em contato o catalisador; (d) passar reagente não-reagido e produto fora do catalisador e, em seguida para cima entre a superfície interna da saia e a superfície externa do catalisador de monólito até que os mesmos alcancem a vedação onde os mesmos são direcionados sobre a extremidade da saia e causados para fluir para baixo entre a superfície externa da saia e a superfície interna do tubo reator onde transferência de calor ocorre; (e) repetir as etapas de (b) a (d) em qualquer portador de catalisador subsequente; e (f) remover produto a partir da saída. [0049] Accordingly, according to a second aspect of the present invention, a process is provided for converting synthesis gas to larger hydrocarbons by contacting a gaseous stream comprising synthesis gas with a monolith Fischer-Tropsch catalyst, said process being carried out in a tubular reactor having an inlet and an outlet, said outlet being located downstream of the inlet, said reactor comprising one or more tubes having located here one or more carriers for said monolith and a half catalyst cooling in contact with said tubes; wherein said catalyst carrier comprises: a container holding a monolith catalyst, said container having a lower surface closing the container and a skirt extending upwards from the lower surface of said container to a position below the location of a seal and spacing thereof, said skirt being positioned such that there is a space between an external surface of the monolith catalyst and the skirt; and a seal located on or near a top surface of the monolith catalyst and extending from the monolith catalyst for a distance that extends beyond an outer surface of the skirt; the referred process that comprises: (a) introducing the gaseous reagents through the inlet; (b) passing said reagents down through at least one said tube to the upper surface of, or the first monolith catalyst where they pass through the monolith catalyst; (c) allowing the reaction to take place as the synthesis gas puts the catalyst in contact; (d) pass unreacted reagent and product out of the catalyst, and then upwards between the inner surface of the skirt and the outer surface of the monolith catalyst until they reach the seal where they are directed over the end of the skirt and caused to flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs; (e) repeat steps (b) to (d) on any subsequent catalyst carrier; and (f) removing product from the outlet.
[0050] [0050] In one arrangement, the monolith catalyst is a solid, in which there is substantially no space within the monolith body that is not occupied by the catalyst. When the monolith is in use in a vertical flow-down reactor, the reagents flow down through the reactor tube, the reagents first come into contact with the top face of the monolith catalyst and flow through them in a direction parallel to the axis the cylinder. The sealing of the container prevents the reagents from flowing around the monolith and assists the direction of the reagents in the catalyst. Reaction will then take place inside the monolith catalyst. The product will then also flow through the monolith in a direction parallel to the axis of the cylinder.
[0051] [0051] Once the reagents and product reach the bottom surface of the catalyst carrier, they are directed towards the carrier's skirt. To facilitate this flow, a foot can be provided inside the carrier on the upper face of the bottom surface such that, in use, the catalyst monolith is supported on the foot and there is a gap between the bottom of the catalyst monolith and the bottom surface of the catalyst catalyst. The skirt extending upwards, then directs the reagents and product upwards between the inner surface of the skirt and the outer surface of the monolith catalyst until they reach the bottom of the seal. They are then directed through the bottom of the seal, over the end of the skirt and they then flow downwards between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs.
[0052] [0052] In an alternative arrangement, the monolith catalyst has a channel that extends longitudinally between it. Generally, the channel will be located on the central axis of the monolith catalyst. Therefore, where the reactor tube has a circular cross section, the monolith catalyst in this arrangement will have an annular cross section. In this arrangement, in use, in a vertical reactor with a downward flow, the reagents flow down through the reactor tube and, therefore, first bring the upper surface of the monolith catalyst into contact. The seal blocks the passage of reagents around the side of the catalyst. Since the path of the reagents is impeded by the catalyst, it will generally take the easiest route and enter the channel in the monolith. The reagents then enter the annular monolith catalyst and pass radially through the catalyst towards the outer surface of the catalyst monolith. During the passage, the reaction of the catalyst monolith occurs. Unreacted reagent and product then flow from the monolith catalyst through the outer surface thereof. The skirt extending upwards, then directs the reagents and product upwards between the inner surface of the skirt and the outer wall of the monolith catalyst until they reach the seal. They are then directed through the bottom of the seal, over the end of the skirt and flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs.
[0053] [0053] In the arrangement where the monolith catalyst includes the channel, the catalyst carrier may include a top surface that will extend over the monolith catalyst, but leave the channel uncovered. This top surface serves to ensure that the reagents do not enter the monolith catalyst from the top, but are directed through the channel during radial flow.
[0054] [0054] The discussion of the specific characteristics of the catalyst carrier above in relation to the first modality also applies in connection with the catalyst carrier for a monolith catalyst of the second modality insofar as the relevant characteristics are present.
[0055] [0055] Any type of carrier is used, in an arrangement more than 40 carriers, preferably more than 41 carriers are located within a single tube. More preferably, about 70 to about 200 carriers can be used. This will allow a reasonable temperature increase of about 10 ° C to about 20 ° C to be maintained over each stage.
[0056] [0056] The radial flow through, or each, catalyst carrier inside the tube means that the length of the gas path is also much shorter when compared to the provisions of the prior art. The total depths of the catalyst on the order of about 2 meters can be reached within a tube up to 20 meters in length at catalyst hourly spatial speeds of around 4000. The lower path means that the total pressure drop achieved is in the order of a lower magnitude than could be experienced with the same catalyst in an axial tube not using the process of the present invention.
[0057] [0057] An advantage of being able to achieve a low total pressure drop by the process of the present invention is that long tubes with high velocities of surface gas, gases containing high amounts of inert recycling or a gas recycling can be accommodated without the drop of pressure and potential during disadvantages of grinding catalyst experienced with high flows through the current fixed bed systems. The ability to accommodate recycling will be capable of full conversion to bottom pass conversions to be achieved in high productivity and catalyst selectivity.
[0058] [0058] The reduced catalyst can be repeatedly and reliably reduced and loaded onto the carrier in a factory and the balance of the container can be filled with wax. The containers can be mounted in connected units that will simplify the reactor loading and, in particular, will mean that operators do not have to contact the catalyst. The non-loading procedure is also simplified since carriers can be promptly unloaded before being taken for reprocessing.
[0059] [0059] In an arrangement of the present invention, a plurality of reactors can be used in parallel.
[0060] [0060] Flow of liquid product separated from the flow out of the reactor will be recovered. In the process of the present invention, unreacted gas leaving the outlet of, or each, reactor can further be treated to remove heat. The removed heat can be reused and / or discarded for cooling. Liquid product separated from the flow out of the reactor will be recovered.
[0061] [0061] In one arrangement, two or more reactors can be located in fluid communication in series with facilities located between each reactor to remove heat. Heat can be reused and / or discarded for cooling. In one arrangement, hydrogen and carbon monoxide containing steam leaving the last stage of a series of interconnected reactors can be recycled at any suitable point in the process. In one arrangement, they will be recycled for the entry of the first reactor.
[0062] [0062] In an alternative arrangement, two or more groups of parallel reactors can be located in series. In this arrangement, groups of parallel reactors are in series communication with facilities located between each group to remove heat. Heat can be reused and / or discarded for cooling. In one arrangement, liquid product can be removed between each stage with hydrogen and carbon monoxide containing flow being passed to a subsequent reactor group in series. Hydrogen and carbon monoxide containing flux leaving the last stage of a series of interconnected reactors can be recycled at any suitable point in the process. In one arrangement, they will be recycled for the entry of the first reactor.
[0063] [0063] Where the process includes a plurality of reaction stages, a flow rich in hydrogen can be fed into the second and / or one or more of any subsequent stages.
[0064] [0064] Any suitable reaction conditions can be used. In one arrangement, the reaction temperature will be about 190 ° C to about 250 ° C. The reaction pressure can be from about 2 MPa (20 bar) to about 8 MPa (80 bar).
[0065] [0065] The present invention will now be described, by way of example, with reference to the attached drawings, in which: Figure 1 is a perspective view from above of the catalyst carrier of the present invention; Figure 2 is a perspective view of the catalyst carrier from below; Figure 3 is a partial cross-section seen from the side; Figure 4 is a simplified diagram of the catalyst carrier of the present invention; Figure 5 is a schematic illustration of a carrier of the present invention from below when located inside a tube; Figure 6 is a schematic cross section of three catalyst carriers located within a tube; Figure 7 is an enlarged cross section of Section A of Figure 6; Figure 8 is a schematic representation of an alternative embodiment of the present invention, illustrating the trajectory; Figure 9 is a schematic representation of a third embodiment of the present invention, illustrating a flow path; and Figure 10 is a schematic representation of the flow path between two stacked carriers of the type illustrated in Figure 9.
[0066] [0066] A catalyst carrier 1 of the present invention is illustrated in Figures 1 to 3. The carrier comprises an annular container 2 having perforated walls 3, 4. The inner perforated wall 3 defines a tube 5. A top surface 6 closes the annular container at the top. It is located at a point across the top of the walls 3, 4 of the annular container 2 such that a flap 6 is formed. A lower surface 7 closes the bottom of the annular container 2 and a surface 8 closes the bottom of the tube 5. The surface 8 is located on a lower plane than that of the lower surface 7. Spacing means in the form of a plurality of depressions 9 are located in the moment on the bottom surface 7 of the annular container 2. Drainage holes 10, 11 are located on the bottom surface 7 and on the surface 8.
[0067] [0067] A seal 12 extends from the upper surface 6 and a vertical collar 13 is supplied coaxially with the tube 5.
[0068] [0068] A vertical wavy skirt 14 surrounds the container 2. The dimples are flattened in the L region through the base of the carrier 1.
[0069] [0069] A catalyst carrier 1 of the present invention is located in a reactor tube 15. The gas flow is schematically illustrated in Figure 4 by the arrows.
[0070] [0070] When a plurality of catalyst carriers of the present invention is located inside a reactor tube 15, they engage as illustrated in Figures 6 and 7. The effect on the trajectory is illustrated in the extended section shown in Figure 7.
[0071] [0071] A catalyst carrier 101 of a second embodiment is illustrated in Figure 8. A bottom surface 102 closes the bottom of container 101. Foot 103 extends upwardly from the bottom surface to support a monolith catalyst 104. A skirt vertical 105 extends from the bottom surface 102. The skirt can be wavy and can be flattened as in a region through the bottom surface 103.
[0072] [0072] A seal 106 is provided to extend from monolith catalyst 104 and interact with reactor tube wall 107. Deflectors 108 extend upward during the seal. These serve to direct the flow and to separate the carrier from the bottom surface of a carrier located above the carrier. The gas flow is schematically illustrated by the arrows.
[0073] [0073] An alternative embodiment of the present invention is illustrated in Figure 9. In this arrangement, monolith catalyst 104 has a longitudinal channel 109 through it. In this arrangement, the foot of the first modality can be omitted. This carrier is similar in layout to the first mode. However, in addition, a top surface 110 is provided to cover the top surface of the monolith catalyst. The gas flow in the arrangement of Figure 9 is illustrated schematically by the arrows.
[0074] [0074] When a plurality of catalyst carriers of the present invention is located within a reactor tube 107, the effect on the trajectory is illustrated in the extended section shown in Figure 10.
[0075] [0075] It will be understood that while the catalyst carrier is described with particular reference for use in a tube of circular cross section, the tube can be of non-circular cross section, for example, it can be a plate reactor. Where the tube has a non-circular cross-section, the carrier will be of the appropriate shape. In this arrangement, in the described mode in which an annular monolith is used, it will be understood that the monolith will not be a circular ring and this term must be constructed accordingly.
[0076] [0076] The present invention will now be discussed with reference to the following example: Example 1
[0077] [0077] Conventional fixed bed reactors, currently in production are capable of producing approximately 695.52 m3 / day (5833 US barrels / day) of Fischer-Tropsch liquids. Public descriptions indicated that these 1200 tonne reactors had a diameter of 7.2 m and contained in addition to 28,000 tubes. A reactor for the process of the present invention for processing feed gas containing hydrogen and carbon monoxide derived from natural gas with a diameter of 5.6 m will produce around 1192.4 m3 / day (10,000 US barrels / day) of Fischer-Tropsch liquids and will contain approximately 2300 axial tubes, each filled with approximately 80 catalyst carriers and approximately 700 tonnes in weight. It will therefore be understood that this represents an improvement of a factor of almost three in the specific weight installed per unit of production over the provisions of the prior art.

权利要求:
Claims (24)
[0001]
Process for converting synthesis gas to higher hydrocarbons, by contacting a gaseous flow comprising synthesis gas with a particulate Fischer-Tropsch catalyst, the process can be carried out in a tubular reactor having an inlet and an outlet, the said outlet being located downstream of the inlet, the reactor comprising one or more tubes having located here one or more carriers for the particulate catalyst and cooling medium in contact with the tubes; wherein the catalyst carrier comprises: an annular container for keeping the catalyst in use, the container having a perforated inner wall defining a tube, a perforated outer wall, a top surface closing the annular container and a lower surface closing the annular container; a surface closing the bottom of the tube formed by an inner wall of the annular container; a skirt extending upwardly from a perforated outer wall of the annular container from a position on or near the bottom surface of the container to a position below the location of a seal; and a seal located on or near the top surface and extending from a container a distance that extends beyond an outer surface of the skirt, characterized by the fact that it comprises: (a) introducing the gaseous reagents through the inlet; (b) passing the reagents down through at least the tube to the upper surface of, or the first catalyst carrier where they pass through the passage defined by the perforated inner wall of the container before radially passing through the catalyst bed to the wall perforated external; (c) allowing the reaction to take place while the gas contacts the catalyst; (d) pass unreacted reagent and product out of the container through the perforated outer wall, and then upwards between the inner surface of the skirt and the outer wall of the annular container until they reach the seal where they are directed over the end of the skirt and caused to flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs; (e) repeat steps (b) to (d) on any subsequent catalyst carrier; and (f) removing product from the outlet.
[0002]
Process according to claim 1, characterized in that the catalyst particles have a diameter of 100 μm to 1 mm.
[0003]
Process for converting synthesis gas to higher hydrocarbons, by contacting a gaseous flow comprising synthesis gas with a monolith Fischer-Tropsch catalyst, the process being carried out in a tubular reactor having an inlet and an outlet, the outlet being located downstream of the inlet, the reactor comprising one or more tubes having located here one or more carriers for the monolith catalyst and cooling medium in contact with the tubes; wherein the catalyst carrier comprises: a container for holding monolith catalyst, the container having a lower surface closing the container and a skirt extending upwards from the lower surface of the container to a position below the location of a seal and spacing thereof, said skirt being positioned such that there is a space between an external surface of the monolith catalyst and the skirt; and a seal located on or near a top surface of the monolith catalyst and extending from the monolith catalyst for a distance that extends beyond an outer surface of the skirt, characterized by the fact that it comprises: (a) introducing the gaseous reagents through the inlet; (b) passing the reagents down through at least one tube on the upper surface of, or the first monolith catalyst where they pass through the monolith catalyst; (c) allowing the reaction to take place as the synthesis gas puts the catalyst in contact; (d) passing unreacted reagent and the product out of the catalyst, and then upwards between the inner surface of the skirt and the outer surface of the monolith catalyst until they reach the seal where they are directed over the end of the skirt and caused to flow down between the outer surface of the skirt and the inner surface of the reactor tube where heat transfer occurs; (e) repeat steps (b) to (d) on any subsequent catalyst carrier; and (f) removing product from the outlet.
[0004]
Process according to any one of claims 1 to 3, characterized in that a plurality of catalyst carriers is stacked within the reactor tube.
[0005]
Process according to any of claims 1 to 4, characterized in that the annular space between the outer surface of the catalyst container and the inner surface of the tube wall is selected to accommodate the required gas flow while maintaining high transfer of heat and low pressure drop.
[0006]
Process according to any one of claims 1 to 5, characterized in that the annular space between the outer surface of the catalyst container and the inner surface of the tube wall is in the range of 3 mm to 10 mm.
[0007]
Process according to any one of claims 1 to 6, characterized in that the tubes have a diameter of 75 mm to 150 mm.
[0008]
Process according to any one of claims 1 to 7, characterized by the fact that more than 41 carriers are located within a single tube.
[0009]
Process according to any one of claims 1 to 8, characterized by the fact that 70 to 200 carriers are located within a single tube.
[0010]
Process according to any one of claims 1 to 9, characterized by the fact that a plurality of reactors are used in parallel.
[0011]
Process according to any one of claims 1 to 10, characterized in that the unreacted gas leaving the outlet of each or each reactor is treated to remove heat.
[0012]
Process according to claim 11, characterized in that the unreacted gas is reused.
[0013]
Process according to any one of claims 1 to 9, characterized by the fact that two or more reactors are located in series.
[0014]
Process according to claim 13, characterized by the fact that the reactors located in series are in fluid communication with the facilities located between each reactor to remove heat.
[0015]
Process according to any one of claims 13 to 14, characterized by the fact that hydrogen and carbon monoxide containing flux leaving the last stage of the series of interconnected reactors are recycled at any suitable point in the process.
[0016]
Process according to claim 15, characterized by the fact that hydrogen and carbon monoxide containing flux leaving the last stage of the series of interconnected reactors are recycled to the first reactor.
[0017]
Process according to claim 9, characterized by the fact that the parallel reactor groups are in series communication with facilities located between each group to remove heat.
[0018]
Process according to either of claims 13 or 16, characterized in that the heat is reused and / or rejected for cooling.
[0019]
Process according to claim 17, characterized in that the liquid product is removed between each group of parallel reactors with hydrogen and carbon monoxide containing flow being passed to a subsequent reaction group in series.
[0020]
Process according to claim 19, characterized by the fact that hydrogen and carbon monoxide containing steam leaving the last stage of a series of interconnected reactors are recycled at any suitable point in the process.
[0021]
Process according to claim 20, characterized by the fact that the flow is recycled at the entrance of the first reactor.
[0022]
Process according to any of claims 9 to 21, characterized in that a flow rich in hydrogen is fed to the second and / or one or more of any subsequent reactors or subsequent reactors.
[0023]
Process according to any of claims 1 to 22, characterized in that the reaction temperature is 190 ° C to 2500C
[0024]
Process according to any of claims 1 to 23, characterized in that the reaction pressure is from 2 MPa (20 bar) to 8 MPa (80 bar).

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WO2012146903A1|2012-11-01|

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CA2789370C|2020-11-24|

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法律状态:
2018-07-31| B25D| Requested change of name of applicant approved|Owner name: JOHNSON MATTHEY DAVY TECHNOLOGIES LIMITED (GB) |

2018-08-21| B25G| Requested change of headquarter approved|Owner name: JOHNSON MATTHEY DAVY TECHNOLOGIES LIMITED (GB) |

2018-12-11| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

2019-08-13| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

2020-07-21| B09A| Decision: intention to grant|

2020-09-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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GBGB1107070.3A|GB201107070D0|2011-04-27|2011-04-27|FT process using can reactor|

GB1107070.3|2011-04-27|

PCT/GB2012/050256|WO2012146903A1|2011-04-27|2012-02-06|Fischer-tropsch process in a radial reactor|

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